Pyridone-methide azo dyestuffs with improved dyeing and printing properties for hydrophobic synethic fiber materials

ABSTRACT

Dyestuffs of the formula    &lt;IMAGE&gt;  (I)  wherein D is the radical of a carbo- or heterocyclic diazo component, X represents O, NH, NT, NCOT, NCCH2T or NSO2T, are preferably suitable, if m=n=l=o, for dyeing and printing hydrophobic synthetic fiber materials and mixtures thereof with naturally occurring fiber materials.

The invention relates to pyridone-methide azo dyestuffs, processes fortheir preparation, their use and coupling components containingpyridone-methide.

Azo dyestuffs which contain a coupling component based onmethylene-triazolopyridines are already known from DE-A 4 020 768 andDE-A 4 329 296. However, these azo dyestuffs still have somedisadvantages in their use. Thus, for example, their build-up capacityand their stability in the dyebath when used for dyeing polyester is notsatisfactory.

Pyridone-methide azo dyestuffs have now been found, which, in the formof the free acid, correspond to the formula (I) or its tautomeric forms##STR2## wherein D is the radical of a carbo- or heterocyclic diazocomponent,

A¹ and A² independently of one another denote H or a substituent typicalfor pyridones,

A³ and A⁴ independently of one another denote an electron-withdrawingradical, or, together with the common C atom, form a cyclicmethylene-active compound,

A⁵ represents H or a radical of the formula T, --OT¹, --NH2, --NHT,--NT₂, --NHCOH, --NHCOT, --N═CH--T, --N═CT₂ or NHSO₂ T,

wherein

T¹ =alkyl, cycloalkyl or aralkyl, and T represents T¹ or can assume themeaning of T² to T⁵, where T² =alkenyl,

T³ =alkinyl,

T⁴ =aryl,

T⁵ =hetaryl or

A¹ and A¹ and/or

A² and A³ and/or

A⁴ and A⁵, together with the particular atoms in between, form anunsaturated, optionally substituted 5- or 6-membered carbo- orheterocyclic radical, with the proviso that if a ring is formed withparticipation of one of the two radicals A³ and A⁴, the radical whichdoes not participate denotes an electron-withdrawing radical,

X represents O, NH, NT, NCOT, NCO₂ T or NSO₂ T,

K.sup.⊕ is --NH₃.sup.⊕, --NHT₂.sup.⊕, --NH₂ T.sup.⊕, --NT₃.sup.⊕ or acycloimmonium ion,

B.sup.⊖ is an anion,

Z is a fibre-reactive radical,

l represents 0 to 2,

m represents 0 to 8 and

n represents 0 to 6.

Preferred pyridone-methide azo dyestuffs are those which correspond tothe formula (I) or its tautomeric form

wherein

A¹ and A² independently of one another denote H or a radical of theformula T, --COH, --CO--T, --CO₂ T, --CN, --CONH₂, --CONHT, --CONT₂,CF₃, --NH₂ --NHT, --NT₂, --NH--COT, --NT--COT, --NHSO₂ T, --NTSO₂ T,--NO₂, --NO, --SO₂ T, --OH, --OT, --OCOT, --OCO₂ T, --OSO₂ T, Cl, Br orI

wherein

T can assume the meaning of T¹, T², T³, T⁴ or T⁵.

The dyestuffs of the formula (I) according to the invention can exist invarious tautomeric forms. One form corresponds, for example, to theformula (I), another corresponds, for example, to the following formula##STR3##

An electron-withdrawing radical is preferably understood as meaning aradical of which the Hammett substituent constant σ (para) is >0, one ofthe two substituents A³ or A⁴ preferably having a σ (para) value >0.300.An appropriate list of Hammett substituent constants is to be found, forexample, in Sykes, Reaktionsmechanismen der organischen Chemie Reactionmechanisms of organic chemistry!, 9th Edition, Weinheim, VCHVerlagsgesellschaft, 1988, or can be determined by known methods.

T¹ preferably represents C₁ -C₂₀ -alkyl, C₄ -C₈ -cycloalkyl or C₆ -C₁₀-aryl-C₁ -C₈ -alkyl, each of which is unsubstituted or substituted byone or more substituents from the group consisting of OH, C₁ -C₁₀-alkoxy, ##STR4## in particular C₁ -C₁₀ -alkoxy-C₂ -C₅ -alkoxy, C₁ -C₅-alkoxy-C₂ -C₅ -alkoxy-C₂ -C₅ -alkoxy, --OCOH, COH, --OCOT, --OSO₂ T,--O(CH₂ CH₂ O)₁₋₆ COT, --OCO₂ T, COT, --SO₂ T, --CO₂ T, --CN, --CONH₂,--CONHT, --CONT₂, --CO₂ H, --SO₂ NH₂, --SO₂ NHT, --SO₂ NT₂, --CF₃, --NO₂and halogen, such as F, Cl, Br and I.

T² and T³ independently of one another preferably represent C₂ -C₂₀-alkenyl or C₂ -C₂₀ -alkinyl, each of which is unsubstituted orsubstituted by one or more substituents from the group of substituentsalready mentioned under T¹.

T⁴ preferably represents C₆ -C₁₆ -aryl, which is unsubstituted orsubstituted by one or more substituents from the group of substituentsalready mentioned under T¹, further possible substituents being --NH₂,--NHT, --NT₂, --NHCOH, --NHCOT, NHSO₂ T, C₂ -C₁₀ -alkenyl, C₂ -C₁₀-alkinyl, C₁ -C₁₀ -alkyl, C₄ -C₈ -cycloalkyl and C₆ -C₁₀ -aryl-C₁ -C₆-alkyl.

T⁵ preferably represents a 5- or 6-membered aromatic heterocyclicradical which contains 1 to 3 identical or different hetero atoms fromthe group consisting of N, O, S, NH, SO and SO₂ and is unsubstituted orsubstituted by one or more substituents from the group of substituentsalready mentioned under T¹ and is optionally fused with one or two arylor hetaryl rings.

Preferred dyestuffs of the formula (I) are those wherein l=1 or 2 andn=0, and m is less than 1, and is preferably 0, which are called"cationic dyestuffs" of the formula (I) below.

Dyestuffs which are likewise preferred are those of the formula (I)wherein l=m=n=0, which are called "disperse dyestuffs of the formula(I)" below.

Dyestuffs which are furthermore preferred are those of the formula (I)wherein o=0 and m and/or n are not equal to 0. These dyestuffs accordingto the invention are called "acid dyestuffs of the formula (I)" below,if n is 0, and "reactive dyestuffs of the formula (1)" below, if n isnot equal to 0.

Acid dyestuffs of the formula I are also understood as meaning thosewhich carry COOH groups and wherein m is 0.

Disperse dyestuffs

Preferred disperse dyestuffs of the formula (I) are those in which

A³ and A⁴ independently of one another represent --CN, --CO₂ T, --CONH₂,--CONHT, --CONT₂, CF₃, --CHO, --COT, --SO₂ T, --SO₃ T⁴, --SO₃ T⁵, SO₂NH₂, SO₂ NHT, SO₂ NT₂, --SOT, --CH═NH, --CH═NT, --CT═NH, --CT═NT,##STR5## --CO--CO₂ T, --NO₂, --NO, T⁴ or T⁵, wherein A³ and A⁴preferably do not simultaneously represent T⁴ and/or T⁵, or

A³ and A⁴, together with the C atom to which they are bonded, representa cyclic methylene-active compound of the formula (IIa) to (IIv), wherethese radicals are shown in the form of ##STR6## wherein V¹ represents Hor a substituent, in particular Cl, Br, CH₃, --CO₂ T¹, --CN, --NO₂,--CF₃ or --SO₂ T¹, and wherein A¹, A², A⁵, D and X have theabovementioned meanings.

Preferred disperse dyestuffs of the formula (I) are those wherein

A¹ represents H, T, --COH, --COT, --CO₂ T, --CN, --CONH₂, --CONH₂,--CONHT, --CONT₂, CF₃, OH or halogen, in particular Cl, Br and I,

A² represents H, T, --COH, --COT, --CN, --CO₂ T, --CONH₂, --CONHT,--CONT₂, --CF₃, --NO₂, --NO, Cl, Br or I,

A³ and A⁴ independently of one another represent --CN, --CO₂ T, --CONH₂,--CONHT, --CONT₂, CF₃, --CHO, --COT, --SO₂ T, --SO₃ T⁴, --SO₃ T⁵, SO₂NH₂, SO₂ NHT, SO₂ NT₂, --SOT, --CH═NH, --CH═NT, --CT═NH, --CT═NT,--CO--CO₂ T, --NO₂, --NO, T⁴ or T⁵, wherein A³ and A⁴ preferably do notsimultaneously represent T⁴ and/or T⁵, or

A² and A³, together with the C atoms in between them, form the radicalof a fused indene ring which is optionally substituted by R¹, or

A³ and A⁴, together with the C atom to which they are bonded, form acarbocyclic or heterocyclic radical of the formula (IIa) to (IIv),

A⁵ denotes H, T¹, T², T³, T₄, --NH₂, --NHT, NT₂, --NHCOT, --NHCOH,--NHSO₂ T or --N═CT₂ or A⁴ and A⁵, together with the atoms of thepyridone ring in between, form a fused ring of the formula ##STR7##wherein the N atom labelled with * corresponds to the pyridone nitrogen,T¹ denotes C₁ -C₁₀ -alkyl, C₅ -C₇ -cycloalkyl or C₆ -C₁₀ -aryl-C₁ -C₆-alkyl, which are optionally substituted by one or more substituentsfrom the group consisting of --OH, --C₁ -C₁₀ -alkoxy, --O (CH₂)₂₋₁₀--O!₁₋₆ -alkyl, in particular --C₁ -C₁₀ -alkoxy-C₂ -C₅ -alkoxy, --C₁ -C₅-alkoxy-C₂ -C₅ -alkoxy-C₂ -C₅ -alkoxy or --O--(CH₂ --CH₂ O)-alkyl,--OCOT, --OSO₂ T, --O--(CH₂ --CH₂ O)₁₋₆ --COT, --COT, --SO₂ T, --CO₂ T,--CN, --CO₂ H, --CONT₂, --CF₃, Cl, Br and I,

T² and T³ independently of one another denote C₂ -C₁₀ -alkenyl oralkinyl, which are optionally substituted by one or more substituentsfrom the group consisting of OH, --C₁ -C₆ -alkoxy, --OCOT, --OCOH, --CO₂T, --CO₂ H, --CN, Cl, Br and I,

T⁴ denotes phenyl, which is optionally substituted by one or moresubstituents such as --C₁ -C₁₀ -alkoxy, --(O--C₂ -C₁₀ -alkylene)₀₋₁--O--(C₂ -C₅ -alkylene)₁₋₆ --O--(C₂ -C₅ -alkyl), in particular C₁ -C₁₀-alkoxy-C₂ -C₅ -alkoxy, C₁ -C₅ -alkoxy-C₂ -C₅ -alkoxy-C₂ -C₅ -alkoxy,--OCOH, --OCOT, --OSO₂ T, --COH, --COT, --SO₂ T, --CO₂ T, --CN, --CF₃,--CCl₃, --NO₂, --NO, --CO₂ H, --CONH₂, --CONHT, --CONT₂, --SO₂ NT², --C₁-C₁₀ -alkyl, optionally substituted by --OH, --CN, --CO₂ --C₁ -C₆-alkyl, Cl, Br or I, --C₂ -C₁₀ -alkenyl, optionally substituted by --OH,--CN, --CO₂ --C₁ -C₆ -alkyl, Cl, Br or I, and --C₂ -C₁₀ -alkinyl,optionally substituted by C₁ -C₁₀ -alkoxy, --OH, --OCOH, --OCOT, Cl, Bror I,

T⁵ denotes thiophene, furan, pyrrole, 1,2-isothiazole, 1,3-thiazole,pyrrazole, oxazole, isooxazole, imidazole, triazole, pyridine,pyridazine, pyrimidine, pyrazine, triazine, oxazine, benzothiazole,benzimidazole, benzoxazole, quinoline, isoquinoline, indole, coumarone,thionaphthene or tetrazole, optionally substituted by 1 to 3substituents such as are already described as substituents for phenyl,

X denotes O, --NCOT, --NCO₂ T or --NSO₂ T,

D denotes a radical of the formula (IIIa) to (IIIu) ##STR8## R¹, R², R³,R⁴, R⁵ and R⁶ independently of one another and denotes H, T, F, Cl, Br,I, --CN, --NO₂, --CH═O, --COT, --CO₂ T¹, --CONH₂, --CONHT, CONT₂, --CF₃,--SO₂ NH₂, --SO₂ NHT, --SO₂ NT₂, --SOT, --SO₂ T, --SO₃ T, --OT, --OH,--OCOT, --OCO₂ T, --OSO₂ T, --NH₂, --NHT, --NT₂, ##STR9## --NHCOH,--NHCOT, --NHSO₂ T or --COCO₂ T, wherein R¹ can additionally denote--N═N--T⁴ or --N═N--T⁵ and

R⁶ can additionally denote ST.

Particularly preferred disperse dyestuffs of the formula (I) are thosewherein

A¹ denotes H, T¹, T⁴ or --CF₃,

A² denotes H, --CN, --CO₂ T¹, --CONHT¹ or --CF₃,

A³ and A⁴ independently of one another denote --CN--, --CO₂ T¹,--CONHT¹, --CF₃, --CHO, --COT, --SO₂ T, --NO₂, --T⁴ or --T⁵, wherein A³and A⁴ do not simultaneously represent T⁴ or T⁵,

A³ and A⁴, together with the C atom to which they are bonded, form acyclic methylene-active compound of the formula (IIa), (IId) or (IIh),where the radicals of the cyclic methylene-active compound are shown inthe form of ##STR10## A⁵ is H, T¹, T² or T₄, or A⁴ and A⁵, together withthe atoms in between, form a fused ring of the formula ##STR11## inwhich the N atom marked with corresponds to the pyridone nitrogen, Ddenotes a radical of the formula ##STR12## wherein R¹ and R⁵independently of one another represent H, CF₃, Cl, Br, --CN, --NO₂,--CO₂ T¹, T¹, T⁵, --SO₂ T¹, --SO₂ T₄, --OT¹, --OT², --OT₄, --OCOT¹,--OCOT₄, --OSO₂ T¹ or --OSO₂ T₄,

R² and R⁴ independently of one another denote H, Cl, Br, --NO₂, --CF₃,T¹, --OT¹, --OT², --OT₄, --OCOT¹, --OCOT₄, OSO₂ T¹ or --OSO₂ T₄,

R³ represents H, Cl, Br, --CN, --NO₂, --CF₃, --CO₂ T¹, T¹, T⁵, --OT¹,--OT², --OT₄, --OCOT, --OCOT₄, --SO₃ T¹ or --SO₂ T₄,

T¹ represents C₁ -C₈ -alkyl, which is optionally substituted by --C₁ -C₈-alkoxy, --C₁ -C₈ -alkoxy-C₂ -C₅ -alkoxy, --OCOT¹, --CO₂ T¹, Cl, Br,--CN or T₄,

T² represents C₂ -C₈ -alkenyl, which is optionally substituted by --C₁-C₈ -alkoxy, --C₁ -C₈ -alkoxy-C₂ -C₅ -alkoxy, --CN, --CO₂ T¹, Cl or Br,

T⁴ represents phenyl, which is optionally substituted by Cl, Br, T¹,OT¹, --CF₃, --NO₂, --CN or --CO₂ T¹,

T⁵ denotes oxazole, phenyloxazole, benzoxazole, thiazole, benzothiazole,thiadiazole or thiophene, which is optionally substituted by Cl, Br, T¹,--NO₂ and/or --CO₂ T¹ and

X denotes O.

Especially preferred disperse dyestuffs of the formula (I) are thosewherein

A¹ represents H, T¹ or --CF₃,

A² denotes H, --CN or --CO₂ T¹,

A³ represents --CN or --CO₂ T¹,

A⁴ denotes A³, or

A³ and A⁴, together with the C atom to which they are bonded, form acyclic methylene-active compound of the formula (IIa) or (IId), wherethe radicals of the cyclic methylene-active compound are shown in theform of ##STR13## A⁵ represents H, T¹ or T², D represents a radical ofthe formula ##STR14## wherein R¹ and R⁵ independently of one anotherdenote H, Cl, Br, --CN, --NO₂, --CO₂ T¹, T¹, --OT¹ or --OT₄,

R² and R⁴ independently of one another denote H, Cl, Br, --NO₂, T¹ or--OT¹,

R³ represents H, Cl, Br, --CN, --NO₂, T¹, --CO₂ T¹ or --OT¹,

T¹ represents C₁ -C₆ -alkyl or C₁ -C₄ -T₄, optionally substituted by C₁-C₆ -alkoxy, --C₁ -C₄ -alkoxy-C₂ -C₅ -alkoxy or --CO₂ T¹,

T² denotes C₂ -C₆ -alkenyl which is optionally substituted by Cl and/orBr,

T⁴ represents phenyl, which is optionally substituted by Cl, Br, --NO₂and/or --CO₂ T¹ and

X denotes O.

The disperse dyestuffs of the formula I according to the invention havea good fastness to light, high tinctorial strength and high affinity onpolyester, and dye polyester in brilliant shades.

Cationic dyestuffs

Preferred cationic dyestuffs of the formula (I) are those wherein A¹ toA⁵ and X have the meanings given for the disperse dyestuffs of theformula (I) and

D represents a radical of the formula (IIIa) to (IIIu), preferably(IIIa), wherein K.sup.⊕ is bonded to one or more positions, as desired,of the radicals D and/or A¹ to A⁵,

B.sup.⊖ denotes an anion,

l represents 1 or 2 and m is preferably 0.

Preferred anions B.sup.⊖ are colourless, organic and inorganic anions,for example fluoride, chloride, bromide, iodide, perchlorate,tetrafluoroborate, hydroxide, hydrogen sulphate, sulphate, dihydrogenphosphate, hydrogen phosphate, phosphate, bicarbonate, carbonate,methyl-sulphate, ethyl-sulphate, cyanate, thiocyanate, tri- andtetrachlorozincate, tetrachloroferrate, hexafluorosilicate and anions ofsaturated or unsaturated aliphatic, cycloaliphatic, aromatic orheterocyclic carboxylic and sulphonic acids, such as formate, acetate,hydroxyacetate, cyanoacetate, propionate, hydroxypropionate, oxalate,citrate, lactate, tartrate, the anion of cyclohexanecarboxylic acid,phenylacetate, benzoate, the anion of nicotinic acid, methanesulphonate,ethanesulphonate, benzenesulphonate, chlorobenzenesulphonate andtoluenesulphonate. If the anions are polyvalent, for example sulphate oroxalate, B.sup.⊖ in formula (I) represents one equivalent of such apolyvalent anion.

Preferred cationic diazo components D are radicals D¹ of the formula##STR15## wherein R¹, K.sup.⊕ and B.sup.⊖ have the abovementionedmeaning and

W denotes a direct bond or a bridge member.

Possible bridge members W are, for example, the following radicals:##STR16## wherein R₇ denotes hydrogen, methyl or ethyl and

m₁ and p₁ independently of one another represent any number from 1 to 4.

Suitable radicals K.sup.⊕ are, for example: ##STR17##

Acid dyestuffs

Preferred acid dyestuffs of the formula (I) are those wherein D, A¹ toA⁵ and X have the meanings given for the disperse dyestuffs of theformula (I), at least one SO₃ H group and/or one COOH group being bondedto at least one of these radicals. Particularly preferred acid dyestuffsof the formula (I) are those wherein m denotes 1 to 4.

Radicals D containing sulphonic acid groups are, for example, radicalsD², wherein D² is a phenyl, phenylazophenyl or naphthyl radical whichcarries 1 or 2 SO₃ H, OSO₃ H or phenyl--SO₂ --NH--SO₂ groups and isoptionally substituted one to four times by C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, trifluoromethyl, C₁ -C₄ -alkylcarbonylamino, benzoylamino, C₁-C₄ -alkylsulphonyl amino, benzenesulphonylamino, cyano, halogen, nitro,C₁ -C₄ -alkylsulphonyl, phenylsulphonyl, tolylsulphonyl,chlorophenylsulphonyl, carboxyl, C₁ -C₄ -alkoxycarbonyl, aminocarbonyl,aminosulphonyl, N-mono- or di-C₁ -C₄ -alkyl-substituted aminocarbonyl or-sulphonyl, or by one benzothiazolyl.

Suitable radicals D² correspond, in the form of their diazo components,for example, to the following:

1-Aminobenzene-2-, -3- or -4-sulphonic acid, 1-aminobenzene-2,4- or-2,5-disulphonic acid, 1-amino-2-methylbenzene-4-sulphonic acid,1-amino-3-methylbenzene-4-sulphonic acid, 1-amino-4-methylbenzene-2- or-3-sulphonic acid, 2-nitroaniline-4-sulphonic acid,4-nitroaniline-2-sulphonic acid, 2-chloroaniline-4- or -5-sulphonicacid, 3-chloroaniline-6-sulphonic acid, 4-chloroaniline-2-sulphonicacid, 1-amino-3,4-dichlorobenzene-6-sulphonic acid,1-amino-2,5-dichlorobenzene-4-sulphonic acid,1-amino-4-methyl-5-chlorobenzene-2-sulphonic acid,1-amino-3-methyl-4-chlorobenzene-6-sulphonic acid,2-amino-4-sulphobenzoic acid, 1-amino-4-acetaminobenzene-2-sulphonicacid, 1-amino-5-acetaminobenzene-2-sulphonic acid,1-amino-2-methoxy-4-nitrobenzene-5-sulphonic acid, 1-aminonaphthalene-2-or 4-sulphonic acid, 2-aminonaphthalene-1-sulphonic acid and the diazocomponents of the formulae ##STR18##

Reactive dyestuffs

Preferred reactive dyestuffs of the formula (I) are those wherein D, A¹to A⁵ and X have the meanings given for the disperse dyestuffs of theformula (I), an SO₃ H group and/or a COOH group preferably being bondedto at least one of these radicals, and wherein one or more identical ordifferent fibre-reactive radicals Z are bonded to at least one of theradicals mentioned.

Reactive dyestuffs of the formula (I) where n=1 to 3 are preferred.

Preferred fibre-reactive radicals are, for example, those of the formula

    --CH═CH.sub.2 or --CH.sub.2 CH.sub.2 --V,

wherein

V=OH or a radical which can be split off under alkaline conditions, forexample OSO₃ H, SSO₃ H, OCOCH₃, OPO₃ H₂, OSO₂ CH₃, SCN, NHSO₂ CH₃, Cl,Br, F, OCOC₆ H₅, OSO₂ --C₆ H₄, N(CH₃)₃ !.sup.⊕ anion.sup.⊖ or anoptionally substituted pyridinium radical (substituents on thepyridinium radical are, in particular, optionally substituted C₁ -C₄-alkyl, COOH, SO₃ H, CN or carboxamide) (anion=for example, Cl,HSO₄.sup.⊖, HCO₃.sup.⊖ and the like), or heterocyclic fibre-reactiveradicals.

Suitable fibre-reactive radicals Z, i.e. those which react with the OHor NH groups of the fibre under dyeing conditions to form covalentbonds, are preferably those which contain at least one reactivesubstituent bonded to a 5- or 6-membered aromatic-heterocyclic ring, forexample to a monoazine, diazine or triazine ring, in particular apyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine orasymmetric or symmetric triazine ring, or to such a ring system whichcontains one or more fused-on aromatic-carboxylic rings, for example aquinoline, phthalazine, cinnoline, quinazoline, quinoxaline, acridine,phenazine or phenanthridine ring system, and which are not bonded to afurther chromophore.

Examples which may be mentioned of the reactive substituents on theheterocyclic radicals are halogen (Cl, Br or F), ammonium, includinghydrazinium, pyridinium, picolinium, carboxypyridinium, sulphonium,sulphonyl, azido (N₃), thiocyanato, thiolether, oxy-ether, sulphinicacid and sulphonic acid.

The following radicals may be mentioned specifically as examples of Z:

2,4-Difluorotriazin-6-yl, 2,4-dichlorotriazin-6-yl andmonohalogeno-sym.-triazinyl radicals, in particular monochloro- andmonofluorotriazinyl radicals, which are substituted by alkyl, aryl,amino, monoalkylamino, dialkylamino, aralkylamino, arylamino,morpholino, piperidino, pyrrolidino, piperazino, alkoxy, aryloxy,alkylthio or arylthio, where alkyl preferably denotes optionallysubstituted C₁ -C₄ -alkyl, aralkyl preferably denotes optionallysubstituted phenyl-C₁ -C₄ -allyl and aryl preferably denotes optionallysubstituted phenyl or naphthyl, and where preferred substituents foralkyl are halogen, hydroxyl, cyano, dialkylamino, morpholino, C₁ -C₄-alkoxy, carboxyl, sulpho or sulphato, and preferred substituents forphenyl and naphthyl are sulpho, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, carboxyl,halogen, acylamino, hydroxyl and amino. Further radicals to be mentionedare 2-amino-4-fluorotriazin-6-yl, 2-methyl amino-4-fluorotriazin-6-yl,2-ethyl amino-4-fluorotriazin-6-yl,2-isopropylamino-4-fluoro-triazin-6-yl,2-dimethylamino-4-fluorotriazin-6-yl,2-diethylamino-4-fluorotriazin-6-yl,2-B-methoxy-ethylamino-4-fluoro-triazin-6-yl,2-β-hydroxyethylamino-4-fluoro-triazin-6-yl,2-di-(β-hydroxyethylamino)-4-fluorotriazin-6-yl,2-carboxymethylamino-4-fluoro-triazin-6-yl,2-di-(carboxymethylamino)-4-fluoro-triazin-6-yl,2-sulphomethyl-methylamino-4-fluoro-triazin-6-yl,2-β-cyanoethylamino-4-fluoro-triazin-6-yl,2-benzylamino-4-fluoro-triazin-6yl, 2-β-phenyl ethylamino-4-fluoro-triazin-6-yl, 2-benzyl-methylamino-4-fluoro-triazin-6-yl,2-(4'-sulphobenzyl)-amino-4-fluoro-triazin-6-yl,2-cyclohexylamino-4-fluoro-triazin-6-yl, 2-(o-, m- orp-methylphenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- orp-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2',5'-disulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- orp-chlorophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- orp-methoxyphenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-methyl-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-methyl-5'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-chloro-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-chloro-5'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-methoxy-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- orp-carboxyphenyl)-amino-4-fluoro-triazin-6-yl,2-(2',4'-disulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(3',5'-disulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-carboxy-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-carboxy-5'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(6'-sulpho-naphth-2'-yl)-amino-4-fluoro-triazin-6-yl,2-(4',8'-disulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl,2-(6',8'-disulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl,2-(N-methyl-N-phenyl)-amino-4-fluoro-triazin-6-yl,2-(N-ethyl-N-phenyl)-amino-4-fluoro-triazin-6-yl,2-(N-β-hydroxyethyl-N-phenyl)-amino-4-fluoro-triazin-6-yl,2-(N-isopropyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-morpho-lino-4-fluoro-triazin-6-yl, 2-piperidino-4-fluoro-triazin-6-yl,2-(4',6',8'-trisulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl,2-(3',6',8'-trisulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl,2-(3',6'-disulphonaphth-1'-yl)-amino-4-fluoro-triazin-6-yl,N-methyl-N-(2,4-dichlorotriazin-6-yl)-carbamyl,N-methyl-N-(2-methylamino-4-chlorotriazin-6-yl)-carbamyl,N-methyl-N-(2-dimethylamino-4-chlorotriazin-6-yl)-carbamyl, N-methyl- orN-ethyl-N-(2,4-dichlorotriazin-6-yl)-aminoacetyl,2-methoxy-4-fluoro-triazin-6-yl, 2-ethoxy-4-fluoro-triazin-6-yl,2-phenoxy-4-fluoro-triazin-6-yl, 2-(o-, m- orp-sulphophenoxy)-4-fluoro-triazin-6-yl, 2-(o-, m- or p-methyl- or-methoxy-phenoxy)-4-fluoro-triazin-6-yl,2-β-hydroxyethylmercapto-4-fluoro-triazin-6-yl,2-phenylmercapto-4-fluoro-triazin-6-yl, 2-(4'-methylphenyl)-mercapto-4-fluorotriazin-6-yl,2-(2',4'-dinitrophenyl)-mercapto-4-fluoro-triazin-6-yl,2-methyl-4-fluoro-triazin-6-yl, 2-phenyl-4-fluoro-triazin-6-yl and thecorresponding 4-chloro- and 4-bromo-triazinyl radicals and thecorresponding radicals obtainable by exchange of halogen with tertiarybases, such as trimethylamine, triethylamine,dimethyl-β-hydroxyethylamine, triethanolamine, N,N-dimethylhydrazine,pyridine, α, β- or γ-picoline, nicotinic acid or isonicotinic acid,sulphinates, in particular benzenesulphonic acid, or hydrogen sulphite,and di- or trihalogenopyrimidinyl radicals, such as2,4-dichloropyrimidin-6-yl, 2,4,5-trichloro-pyrimidin-6-yl,4,5-dichloro-pyrimidin-6-yl, 2,4-dichloropyrimidin-6-yl,4,5-difluoropyrimidin-6-yl, 4-fluoro-5-chloropyrimidin-6-yl,2,4-difluoro-5-chloropyrimidin-yl and2,3-dichloro-quinoxaline-5-carbonyl and2,3-dichloroquinoxaline-6-carbonyl.

Suitable diazo components for the reactive dyestuffs of the formula (I)are, inter alia, those wherein D has the abovementioned meaning, andrepresents D² with the meaning given there, and furthermore representsreactive diazo components D³, wherein D³ denotes ##STR19## wherein R⁸can assume the meanings given for R¹ and additionally can denote SO₃ H,OSO₃ H or COOH and

R⁹ represents H, T¹ or T⁴.

The dyestuffs according to the invention, in particular dispersedyestuffs of the formula (I), can be prepared by coupling diazotizedamines which, as the amine, correspond to the formula (IV)

    D--NH.sub.2                                                (IV)

to coupling components of the formula (V) ##STR20## wherein A¹ to A⁵, Dand X have the abovementioned meaning and E represents a substituentwhich can be replaced by electrophilic substitution, such as, forexample, H, --CO₂ H, --CH₂ OH, --SO₃ H, --CH═O, --COT, ##STR21##

Such a coupling process with displacement of a substituent is described,for example, in GB 2 036 775 and Jp 58 157 863.

The coupling can be carried out in an aqueous and non-aqueous solvent.Non-aqueous solvents which may be mentioned are alcohols, such asmethanol, ethanol, propanol, butanol, pentanol and the like, dipolaraprotic solvents, such as DMF, DMSO and NMP, and water-immisciblesolvents, such as toluene and chlorobenzene.

The coupling is preferably carried out in the stoichiometric ratio, butit may be advantageous and in some cases appropriate for economicreasons to employ the cheaper components in an excess of up to 30%.

The coupling is carried out at temperatures between -30° and 100° C.,temperatures from -10° to 30° C. being preferred and temperatures from-5° to 10° C. being particularly preferred.

The coupling can be carried out in an acid medium and also in analkaline medium. pH values >0.5 and <14 are preferred, particularlypreferably >1.0 and <12 and especially preferably >3.0 and <11.0.

An oxidative coupling of (hetero)aromatic hydrazines of the formula (VI)

    D--NH--NH.sub.2                                            (VI)

to coupling components of the formula (V) is furthermore also possible,which is characterized in that VI is coupled oxidatively in the presenceof V. Methods of oxidative coupling are described, for example, inHouben-Weyl "Methoden der organischen Chemie Methods of organicchemistry!", Volume 10/3, page 360 et seq., and also in EP 201 892 orChem. Express 1988, 3(7), 423-6.

A process for the preparation of dyestuffs of the formula (I) wherein Xdenotes O is furthermore preferred, which is characterized in thatcompounds of the formula (VII), which can exist in the tautomeric formsof the formula (VIIa) and (VIIb) ##STR22## wherein G¹ denotes O, NH orNT, preferably O,

G² represents --OT, --NH₂ or --NHT, preferably OT¹, and

D and A¹ have the abovementioned meanings, are subjected to acondensation reaction with enamines of the formula (VIII) ##STR23##wherein A² to A⁵ have the abovementioned meanings.

This condensation reaction is preferably carried out, in the case of thedisperse dyestuffs of the formula (I), in organic solvents, inparticular dipolar aprotic solvents. Examples which may be mentioned arealcohols, such as methanol and ethanol, and, on the other hand, DMF,DMSO and NMP.

The condensation reaction is carried out at temperatures from -10° to200° C., preferably from 0° to 150° C., in particular at 20° to 130° C.

The condensation reaction is preferably carried out in the presence ofbases, such as, for example, secondary and tertiary amines and alkalimetal alcoholates. The amount of base varies here between catalytic andfive times the molar amounts. 1 to 3 mol of base are preferablyemployed. Suitable bases are, for example, triethylamine, sodiummethylate, sodium ethylate, sodium butylate, sodium amylate, K₂ CO₃, Na₂CO₃, DBU (diazabicycloundecene) and DBN (diazabicyclononene).

The compounds of the formula (VII) are known in some cases from DE-A-2015 172, or they can be prepared by known methods.

The enamines of the formula (VIII) are known in most cases and/or areaccessible by "dimerization" or "codimerization" of cyanoacetic acidderivatives in accordance with the equation ##STR24## cf., for example,Liebigs Ann. Chem. 1987, 1131 to 1132 and literature cited therein.

Preferred enamines of the formula (VIII) correspond to the formulae(VIIIa) to (VIIIc). ##STR25##

Another method of preparation of enamines of the formula (VIII) is thereaction of iminoesters with methylene-active compounds in accordancewith Liebigs Ann. Chem. 1986, 533 to 544 ##STR26## wherein T¹ has theabovementioned meaning.

Compounds of the formula (V) are known in some cases from AU 491 554,Aust. J. Chem. 29 (1976), 1039-50 and J. Am. Chem. Soc. 81, 2452.

The invention furthermore relates to compounds of the formula (V)##STR27## wherein E and X have the abovementioned broadest meanings,

A¹ and A² independently of one another denote H or a radical of theformula T, --COH, --CO--T, --CO₂ T, --CN, --CONH₂, --CONHT, --CONT₂,CF₃, --NO₂, NO, --SO₂ T, --OH, --OT, --OCOT, --OCO₂ T, --OSO₂ T, Cl, Bror I, wherein

T can assume the meaning of T¹, T², T³, T⁴ or T⁵, where

T¹ =alkyl, cycloalkyl or aralkyl,

T² =alkenyl,

T³ =alkinyl,

T⁴ =aryl,

T⁵ =hetaryl,

A³ and A⁴ independently of one another denote an electron-withdrawingradical, or together with the common C atom form a cyclicmethylene-active compound,

A⁵ represents H or a radical of the formula T, --OT¹, --NH₂, --NHT,--NT₂, --NHCOH, --NHCOT, --N═CH--T, --N═CT₂ or NHSO₂ T, or

A¹ and A² or

A² and A³, together with the particular atoms in between, form anunsaturated, optionally substituted 5- or 6-membered carbo- orheterocyclic radical, where, in the case of ring formation withparticipation of one of the radicals A³ or A⁴, the other particularradical denotes an electron-withdrawing radical, and where the radicalsA¹ to A⁵ optionally carry one or more SO₃ H, COOH or K.sup.⊕ and B.sup.⊖groups, wherein K.sup.⊕ and B.sup.⊖ have the above meanings.

Preferred compounds of the formula (V) are those wherein

A¹ denotes H, T¹, T⁴ or CF₃,

A² denotes H, --CO₂ T¹, --CN, --CONH₂, --CONHT, --CO₂ T² or --CONT¹ ₂,

A³ denotes --CO₂ T, --CN, --CONH₂, --CONHT, --CONT¹ ₂ or --CO₂ T²,

A⁴ denotes --CO₂ T¹, --CN, --CONH₂, --CONHT, --CONT¹ ₂ or --CO₂ T²,

A⁵ denotes H, T¹ or T² or

A³ and A⁴, together with the common C atom, denote a cyclicmethylene-active compound of the formula (IIa) or (IId) and

E denotes H.

Particularly preferred compounds of the formula (V) are those wherein

A denotes H, CH₃, C₆ H₅ or CF₃,

A² denotes H, CO₂ C₁ -C₁₀ -alkyl, --CO₂ C₂ -C₁₀ -alkenyl,

A³ and A⁴ independently of one another denote --CO₂ C₁ -C₁₀ -alkyl,--CO₂ C₂ -C₁₀ -alkenyl or --CN,

A⁵ denotes H or C₁ -C₁₀ -alkyl and

E denotes H.

The invention furthermore relates to a process for the preparation ofthe compounds of the formula (V) in the form of the compound Va or Vb,wherein X represents O or NH, characterized in that acetic acidderivatives of the formula IXa or IXb are reacted with enamines of theformula (VIII): ##STR28## wherein A¹ to A⁵, E, G¹ and X have theabovementioned broadest meaning, wherein

A⁵ preferably represents H, and

G² has the abovementioned meaning. Preferably,

G¹ represents O,

E represents H and

G² represents OT¹.

The reaction is preferably carried out in organic solvents. Suitablesolvents are alcohols, dipolar aprotic solvents, such as DMF,water-immiscible solvents and esters, above all acylacetic esters, suchas, for example, methyl or ethylacetoacetate.

Water-immiscible solvents offer the advantage that the water formed inthe reaction in the case where G¹ =O can be removed azeotropically withthem from the reaction mixture.

A particularly preferred embodiment, especially in the case of lessreactive enamines of the formula (VIII), i.e. wherein A² represents--CO₂ T, comprises working with an excess of (IX) as thesolvent--without using further cosolvents. This excess of (IX) over(VIII) is preferably 5 to 500% by weight.

The reaction is preferably carried out at temperatures from 0° to 200°C., preferably 20° to 150° C., particularly preferably at 70° to 120° C.

The reaction can be accelerated by catalysts. Suitable catalysts areacids, such as, for example, glacial acetic acid, and acid-base pairs,such as β-alanine-glacial acetic acid, ammonium acetate,piperidine-glacial acetic acid and morpholine-glacial acetic acid.

Inorganic and organic bases are furthermore suitable as catalysts orreaction partners. Bases which may be mentioned are sodium hydroxide,sodium ethylate, potassium ethylate, triethylamine, piperidine,morpholine and ethanolamine, such as are also employed in condensationreactions of CH-acid compounds with acetylacetone and the like.(Compare: Monatshefte fur Chemie 95, 1201, 1473 (1964) and J. Chem. Eng.Data 29, 101).

Particularly suitable bases, especially with less reactive enamines ofthe formula (VIII), wherein A² represents --CO₂ T, are stericallyhindered strong bases, such as, for example, potassium tert-butylate,and sterically hindered N bases, such as, for example,diazabicycloundecene (DBU) and diazabicyclononene (DBN).

The reaction can be carried out under normal pressure and also underincreased or reduced pressure. It is preferable, especially in the caseof less reactive enamines of the formula (VIII), to work under reducedpressure under pressures of <200 mbar, in particular <100 mbar, so thatthe cleavage products water and alcohol formed from the condensationreaction with the preferred acetic acid derivative of the formula (IX),the alkylacetoacetate, can be removed rapidly from the reaction mixture.

In contrast to the acid catalysts and acid-base pairs, bases arepreferably employed in the stoichiometric ratio or in an excess. Theexcess can be 1 to 500%.

A process which is also preferred is a process for the preparation ofcompounds of the formula V which correspond to the formula X which ischaracterized in that a trifluoroacetic ester of the formula (XI), whichrepresents a particular embodiment of the acetic acid derivative of theformula (IX), is subjected to a condensation reaction with dimericcyanoacetic acid esters of the formula (XII), which represent aparticular embodiment of the enamines of the formula (VIII) ##STR29##wherein T¹ has the abovementioned broadest meaning. The reactionconditions are the same as those described above for less reactiveenamines.

The invention also relates to a process for the preparation of compoundsof the formula (V), wherein A⁵ represents T¹, T² or T³, which ischaracterized in that pyridinium salts of the formula (XIII) ##STR30##wherein E, A¹ and A² have the abovementioned broadest meaning,

An.sup.⊖ is an anion, which can assume, for example, the meanings givenfor B.sup.⊖, and in particular represents Cl.sup.⊖, Br.sup.⊖, I.sup.⊖,T¹ OSO₃.sup.⊖ or TSO₃.sup.⊖,

A⁵ represents T¹, T² or T³ and

Y¹ and Y² independently of one another represent a leaving group, suchas F, Cl, Br, I, --OSO₂ T, --OT, --ST or --SO₂ T, are reacted withcompounds of the formula (II) ##STR31## wherein A³ and A⁴ have theabovementioned broadest meaning, to give compounds of the formula (XIV)##STR32## and these are reacted with compounds of the formula (XV)

    XH.sub.2                                                   (XV)

wherein

X represents O, NH, NT¹, NCOT, NCO₂ T or NSO₂ T, to give compounds ofthe formula (V) wherein A⁵ represents T¹, T² or T³.

In a preferred embodiment of this process,

E represents H

A¹ represents H or T¹,

A² represents H,

Y¹ represents Cl, Br or I,

Y² represents Cl, Br, I or --OT¹ and

H₂ X represents H₂ O, NH₃, H₂ NT¹ or H₂ NSO₂ T, in particular H₂ O.

In a particular embodiment of the process, A⁵ represents T¹ or T²,particularly preferably T¹, and especially preferably methyl or ethyl.

The reaction of the compounds of the formulae (XIII) and (II) can becarried out in water or in aqueous or non-aqueous solvents, such as, forexample, alcohols or dipolar aprotic solvents.

Suitable temperatures are -20° to 150° C., preferably 0° to 100° C., inparticular 15° to 80° C.

This reaction is preferably carried out in the presence of inorganic ororganic bases. Suitable bases are alkali metal hydroxides, alkali metalalcoholates, alkali metal hydrides, alkali metal oxides, alkaline earthmetal oxides, alkali metal carbonates, alkali metal bicarbonates, alkalimetal hydrides or organic N bases, such as tertiary amine(triethylamine, DBU, DBN and the like). These bases are preferablyemployed in stoichiometric amounts, i.e. twice the molar amounts in(XIII).

Instead of the compound (II), the corresponding anion of (II) ##STR33##wherein A³ and A⁴ have the abovementioned broadest meaning and Cat.sup.⊕represents a cation, such as, for example, those of lithium, sodium andpotassium, can also be employed for the reaction with pyridinium salts(XIII).

The second reaction stage--conversion of (XIV) into (V)--is alsopreferably carried out in the presence of bases.

In the case where the compounds of the formula (XV) correspond to theamines --NH₃ or H₂ NT¹, these reactants are also preferably employedsimultaneously as the base and, where appropriate, also as the solvent.

If X represents O, alkali metal hydroxides, alkaline earth metalhydroxides and/or alkali metal carbonates are preferably employed asbases.

If X represents --NCOT, --NCO₂ T or --NSO₂ T, the corresponding anion,for example C₆ H₅ SO₂ NH.sup.⊖, is preferably employed as the base andreactant.

Further preferred bases here are also inert bases and stericallyhindered bases. Suitable bases are, for example, tertiary amines, suchas triethylamine, DBU and DBN. Preferably, at least 2 molar equivalentsof base are employed.

Suitable solvents are preferably organic solvents which are inert underthese conditions, such as, for example, dipolar aprotic solvents,aromatic hydrocarbons, such as toluene, and chlorinated hydrocarbons,such as chlorobenzene.

Depending on the nucleophilicity of the educt H₂ X or of thecorresponding base, the reaction takes place at temperatures between-20° C. and 200° C., preferably 0° C. and 150° C.

The pyridinium salts of the formula (XIII) required are accessible in asimple manner by quaternization of corresponding pyridines (XVI) withalkylating agents A⁵ -An, such as, for example, dimethyl sulphate, inaccordance with the reaction ##STR34##

For ecological and economic reasons, the quaternization and also thereaction with compounds (II) and, where appropriate, also the reactionwith XH₂ are preferably carried out without intermediate isolation.

Another process for the preparation of the coupling components of theformula (V), wherein A⁵ represents T, is characterized in that pyridinederivatives of the formula (XVII) are reacted with compounds of theformula (II): ##STR35## wherein X=O, A¹ to A⁴ and E have theabovementioned meaning and A⁵ represents T.

In a preferred embodiment of this process, E represents H,

A¹ represents H or T¹, especially preferably H,

A² represents H,

Y¹ represents F, Cl, Br, I, OSO₂ T, SO₂ T, --ST or OT, particularlypreferably Cl, Br or --SO₂ T, and especially preferably Cl, and

A⁵ represents T¹ or T², particularly preferably T¹, and especiallypreferably methyl or ethyl, and

one of the two radicals A³ and A⁴ preferably represent --CN, --CO₂ T,--CONH₂, --CONHT, --CONT², --CHO, --COT, --SO₂ T, --SO₂ NH₂, --SO₂ NHT,--SO₂ NT₂, --NO₂, T⁴ or T⁵,

while the other preferably represents --CN, --CO₂ T, --CONH₂, --CONHT or--CONT², or

A³ and A⁴, together with the C atom to which they are bonded, form acyclic methylene-active compound of the formulae (IIa to IIv),preferably (IIa to IIh), in particular (IIa and IId).

Suitable solvents for this reaction are preferably organic solvents.Both water-miscible and water-immiscible solvents are possible here.

The reaction temperatures are preferably in the range from 20° to 250°C., preferably 50° to 150° C.

Bases are preferably added, in particular more than 2 molar equivalentsof base, based on the starting material of the formula (XVII).

Suitable bases are inorganic or organic in nature. For example, tertiaryamines, such as triethylamine, DBU and DBN, are suitable.

Another process for the preparation of coupling components of theformula (V), which correspond to the formula (XX), wherein A⁵ representsT¹, T² or T³, is characterized in that 2-methylpyridones of the formula(XVIII) are reacted with phthalic acid esters of the formula (XIX) inthe presence of bases ##STR36## wherein A¹, A², E, T¹ and V¹ have theabovementioned broadest meaning.

In a preferred embodiment of this process

E represents H,

A⁵ represents T¹, particularly preferably methyl or ethyl,

A¹ represents H, T¹ or T⁴, particularly preferably T¹, and especiallypreferably methyl, and

V¹ represents H.

In this reaction, the phthalic acid ester of the formula (XIX)simultaneously serves as the solvent.

Suitable bases are preferably alkali metal alcoholates, which arepreferably employed in at least equimolar amounts, based on (XVIII).

The reaction temperature is in general 50° to 200° C., preferably 100°to 160° C., the alcohol T¹ OH formed preferably being distilled off fromthe reaction.

The removal of the alcohol can be promoted by working under reducedpressure.

The product can be isolated in crystalline form by discharging themixture onto water and acidifying the aqueous phase.

The dyestuffs of the formula (I) according to the invention aresuitable, depending on the presence of substrate-specific substituents,for dyeing and printing naturally occurring and synthetic materials,such as, for example, cellulose fibres, cotton, wool, silk, polyamide,polyacrylonitrile, polyester or polyolefins.

Thus, for example, the dyestuffs described as disperse dyestuffs of theformula (I) are particularly suitable, either as such or also as amixture with other disperse dyestuffs, for dyeing and printinghydrophobic synthetic fibre materials and mixtures thereof withnaturally occurring fibre materials.

Possible hydrophobic synthetic materials are, for example: cellulose21/2-acetate, cellulose triacetate, polyamides and, in particular,polyesters, such as, for example, polyethylene glycol terephthalate.Mixtures thereof with naturally occurring fibre materials are, forexample, cotton, regenerated cellulose fibres or wool.

They are furthermore suitable for dyeing and, where appropriate,printing waxes, oils and plastics such as polymethacrylate, PVC,polystyrene or ABS.

They are also suitable for textile and non-textile thermotransferprinting, for example by means of a thermal head or also by means ofink-jet processes.

The compounds described as cationic dyestuffs of the formula (I) in thecontext of this Application are preferably used for dyeing or printingacid-modified polyester or polyamide, but preferably for dyeing andprinting polyacrylonitrile.

Moreover, they can also be employed for dyeing paper.

The compounds described as reactive dyestuffs of the formula (I) in thecontext of this Application are preferably used for dyeing and printingmaterials containing hydroxyl groups, such as, for example, cellulosefibres, in particular cotton, and for dyeing and printing materialscontaining amide groups, such as, for example, wool, silk and polyamide.

The compounds described as acid dyestuffs of the formula (I) in thecontext of this Application are preferably employed for dyeing andprinting naturally occurring or synthetic polyamide and base-modifiedpolyacrylonitrile fibres. They can moreover be employed for dyeingpaper.

The dyestuffs can be applied here from aqueous or non-aqueous liquors oralso in printing processes.

They produce strong dyeings with good general fastnesses.

Neutral dyestuffs produce particularly brilliant dyeings of highfastness to light on polyester. The shades range here from yellow toblue, the particular strength lying in brilliant red shades.

If A³ and A⁴ in the formulae mentioned in the Examples have differentmeanings, the configuration on the carbon atom to which they are bondedis not intended to be specified by the formulae. The enamines3-amino-2-cyano-pentene-dioic acid diesters (Δ 2-amino-1-cyanoglutaconicacid diesters) used in the Examples were prepared by processes analogousto that described in Liebigs Anm. Chem. 1987, 1131, in which suchenamines are described as having the Z configuration.

EXAMPLES Example 1

Preparation of the dyestuff of the formula ##STR37##

5.5 ml of 40% strength nitrosylsulphuric acid were added to 6.1 g of4-methyl-2-nitroaniline, dissolved in 20 ml of propionic acid and 40 mlof glacial acetic acid, at 0°-5° C. in the course of 10 minutes. Themixture was stirred at 0°-5° C. for a further 2 hours. 20 ml of 10%strength aqueous amidosulphonic acid solution and then, at 5° C., theabove diazotization reaction mixture were added to a solution, broughtto pH 7 by means of a few ml of concentrated sodium hydroxide solution,of 5.8 g of 6-hydroxy-3-cyano-4-methyl-2(1H)-pyridinylidene!-malononitrile in 400 ml of water.The mixture was allowed to warm to room temperature in the course of 16hours, the precipitate was filtered off with suction and the filter cakewas washed neutral with water.

Yield: 9.3 g

MS, m/z (%): 361 (72) M⁺. !, 315 (18) M⁺. --NO₂ ! 152 (100)

UV (DMF): λ_(max) =537 nm

The dyestuff dyes polyester in a bluish-tinged red with good fastnessproperties.

The dyestuffs of the formula ##STR38## listed below, which likewise dyepolyester with good properties, were obtained analogously to Example 1.

                  TABLE 1                                                         ______________________________________                                                                           Colour                                     Ex.                                shade on                                   No.  D                    λ.sub.max nm                                                                    polyester                                  ______________________________________                                         2                                                                                  ##STR39##           535 (CH.sub.3 CN)                                                                      Ruby                                        3                                                                                  ##STR40##           535 (CH.sub.3 CN)                                                                      Ruby                                        4                                                                                  ##STR41##                    Yellowish- tinged red                       5                                                                                  ##STR42##                    Yellowish- tinged red                       6                                                                                  ##STR43##                    Yellowish- tinged red                       7                                                                                  ##STR44##           536 (CH.sub.3 CN)                                                                      bluish- tinged pink                         8                                                                                  ##STR45##                    Bluish- tinged red                          9                                                                                  ##STR46##                    Bluish- tinged red                         10                                                                                  ##STR47##           518 546 sh (CH.sub.3 CN)                                                               Ruby                                       11                                                                                  ##STR48##                    Bluish- tinged red                         12                                                                                  ##STR49##                    Bluish- tinged scarlet                     13                                                                                  ##STR50##                    Bluish- tinged red                         14                                                                                  ##STR51##                    Scarlet                                    15                                                                                  ##STR52##                    Yellowish- tinged red                      16                                                                                  ##STR53##                    Yellowish- tinged red                      17                                                                                  ##STR54##                    Violet                                     18                                                                                  ##STR55##           494 516 sh (CH.sub.3 CN)                                                               Yellowish- tinged red                      19                                                                                  ##STR56##           518 546 sh (CH.sub.3 CN)                                                               Bluish- tinged red                         20                                                                                  ##STR57##                    Red-violet                                 21                                                                                  ##STR58##                    Reddish- tinged violet                     22                                                                                  ##STR59##           507 (CH.sub.3 CN)                                                                      Bluish- tinged red                         23                                                                                  ##STR60##           518 546 sh (CH.sub.3 CN)                                                               Bluish- tinged red                         24                                                                                  ##STR61##           518 546 sh (CH.sub.3 CN)                                                               Bluish- tinged red                         25                                                                                  ##STR62##                    Red-violet                                 26                                                                                  ##STR63##           507 531 sh (CH.sub.3 CN)                                                               Bluish- tinged red                         27                                                                                  ##STR64##                    Red-violet                                 28                                                                                  ##STR65##           535 (CH.sub.3 CN)                                                                      Ruby                                       29                                                                                  ##STR66##                    Bluish- tinged red                         30                                                                                  ##STR67##                    Bluish- tinged red                         ______________________________________                                    

Example 31

Preparation of6-hydroxy-3-cyano-4-methyl-2-(1H)-pyridinylidene!malononitrile ##STR68##

15.4 g of the sodium salt of 2-amino-1,2,3-tricyano-propene("malononitrile dimer") were heated at the boil under reflux with 13 gof ethyl acetoacetate, 1 ml of piperidine and 6 g of glacial acetic acidin 100 ml of ethanol for 16 hours. After cooling, a beige powder wasfiltered off with suction and washed with ethanol. Yield: 14.5 g

IR v (cm⁻¹): 3430, 2185 (C.tbd.N), 2205(C.tbd.N), 2225(C.tbd.N) 1668,1566, 1356, 832

¹ H-NMR (d₆ -DMSO, 300 MHz, ppm): δ=2.15 (s, 3H, CH₃), 5.70 (s, 1H),7.30 (s, 2H, OH, NH)

MS, m/z (%): 198 (42 M⁺. !, 170 (13) M⁺. -H₂ O! 155 (100)

Example 32

Preparation of the dyestuff of the formula ##STR69##

8.3 ml of 40% strength nitrosylsulphuric acid were added to 6.6 g ofmethyl 2-aminobenzoate, dissolved in 15 ml of propionic acid and 30 mlof glacial acetic acid, at 0°-5° C. in the course of 10 minutes. Themixture was stirred at 0° C. for a further 2 hours.

70 ml of the solution, described in the following Example No. 33, of thecoupling component ethyl6-hydroxy-4-methyl-3-(ethoxycarbonyl)-2(1H)-pyridinylidene!-cyanoacetate(about 0.5 mol) in 550 ml of dimethylformamide were topped up to 200 mlwith ethanol, 2 g of amidosulphonic acid were added and coupling wasthen carried out with the above diazotization mixture at 0° C., with theaddition of 50 g of ice. The mixture was subsequently stirred for 15hours and the product was filtered off with suction and washed withwater.

Yield: 15.3 g. After recrystallization from dimethylformamide, 6.3 gremained.

The dyestuff dyed polyester in a brilliant orange with good fastnessproperties.

MS, m/z (%): 454 (100) M⁺. !, 422 (8) 409 (8), 350 (25), 349 (16), 322(25) 293 (18)

λ_(max) : 483 nm (CH₃ CN)

Example 33

Preparation of coupling component of the formula ##STR70##

A solution of 113 g of diethyl 3-amino-2-cyano-pentenedioate ("dimericethyl cyanoacetate", 0.5 mol), 90 ml of ethyl acetoacetate and 76 g ofdiazabicyclo-undecene (DBU) in 500 ml of dimethylformamide was stirredat 120° C. for 11 hours. A further 25 ml of ethyl acetoacetate wereadded and the mixture was stirred at 120° C. for a further 9 hours, thereadily volatile cleavage products being distilled off. The mixture wastopped up to a volume of 800 ml with 50 ml of dimethylformamide and thebrown solution was employed directly for the coupling reaction. A samplewas freed from the solvent under 20 mbar/100° C. The brown oil whichremained showed the following mass spectrum:

MS, m/z (%): 292 (27) M⁺. !, 247 (14), 218 (27), 192 (42), 174 (58), 164(35), 152 (65), 151 (51), 148 (43), 96 (33), 42 (64), 29 (100)

The dyestuffs of the formula ##STR71## listed below (Table 2), whichlikewise dye polyester with good fastness properties, were obtainedanalogously to Example 32.

                  TABLE 2                                                         ______________________________________                                                                         Colour shade on                              Ex. No.                                                                             D                 λ.sub.max nm                                                                    polyester                                    ______________________________________                                        34                                                                                   ##STR72##        507 (DMF)                                                                              Bluish-tinged red                            35                                                                                   ##STR73##        515 (CH.sub.3 CN)                                                                      Blusih-tinged red                            36                                                                                   ##STR74##                 Scarlet                                      37                                                                                   ##STR75##        495 (CH.sub.3 CN)                                                                      Scarlet                                      38                                                                                   ##STR76##                 Orange                                       39                                                                                   ##STR77##        483 (CH.sub.3 CN)                                                                      Orange                                       40                                                                                   ##STR78##                 Orange                                       41                                                                                   ##STR79##                 Orange                                       42                                                                                   ##STR80##        507 (CH.sub.3 CN)                                                                      Pink                                         43                                                                                   ##STR81##        507 (CH.sub.3 CN)                                                                      Bluish-tinged red                            44                                                                                   ##STR82##                 Scarlet                                      45                                                                                   ##STR83##                 Red                                          ______________________________________                                    

Example 46

Preparation of the dyestuff mixture of the formula ##STR84##

11.7 g of ethyl 2-phenylazo-acetoacetate and 11 g of the sodium salt ofdimethyl 3-amino-2-cyano-pentenedioate ("dimeric methylcyanoacetate")were stirred in 50 ml of dimethylformamide at 90° C. for 10 hours. Afteraddition of a further 2.2 g of dimeric methylcyanoacetate, the mixturewas heated at 100° C. for a further 6 hours. After cooling to roomtemperature, 100 ml of methanol, 6 g of 30% strength hydrochloric acidand 15 ml of water were added. The product was filtered off with suctionand washed with methanol.

Yield: 4.1 g

The dyestuff dyed polyester in a brilliant scarlet with good fastnessproperties.

MS, m/z (%) 382 (22) M⁺. ethyl ester! 369 (20), 368 (89) M⁺. methylester!, 337 (9) M⁺. methyl ester --OCH₃ !, 310 (9), 276 (7), 231 (19),199 (11), 105 (19) 93 (30), 92 (28), 77 (100)

λ_(max) : 486 nm (CH₃ CN)

The following dyestuffs of the formula ##STR85## which likewise dyepolyester with good fastness properties, were obtained analogously toExample 46.

                  TABLE 3                                                         ______________________________________                                                                           Colour                                     Ex.                                shade on                                   No.  D                    λ.sub.max (nm)                                                                  polyester                                  ______________________________________                                        47                                                                                  ##STR86##                    Ruby                                       48                                                                                  ##STR87##                    Bluish- tinged red                         49                                                                                  ##STR88##           512 (CH.sub.3 CN)                                                                      Red                                        50                                                                                  ##STR89##           498 (CH.sub.3 CN)                                                                      Scarlet                                    51                                                                                  ##STR90##           485 (CH.sub.3 CN)                                                                      Orange                                     52                                                                                  ##STR91##                    Orange                                     53                                                                                  ##STR92##           512 (CH.sub.3 CN)                                                                      Red                                        54                                                                                  ##STR93##                    Bluish- tinged red                         55                                                                                  ##STR94##           515 (CH.sub.3 CN)                                                                      Bluish- tinged red                         56                                                                                  ##STR95##           516 (CH.sub.3 CN)                                                                      Bluish- tinged red                         57                                                                                  ##STR96##           483 (CH.sub.3 CN)                                                                      Orange                                     58                                                                                  ##STR97##           483 (CH.sub.3 CN)                                                                      Orange                                     59                                                                                  ##STR98##           483 (CH.sub.3 CN)                                                                      Orange                                     ______________________________________                                    

Example 60

Preparation of the coupling component of the formula ##STR99##

Diamyl 3-amino-2-cyano-pentenedioate ("dimeric amylcyanoacetate") wasprepared analogously to Junek, Monatschefte fur Chemie, 101 1979! 1208.

12.2 ml of diazabicyclononene (DBN) and 34.4 g of amyl acetoacetate wereadded to 31 g of diamyl 3-amino-2-cyano-pentenedioate and the mixturewas heated at 80° C. for 4 hours. A further 8.6 g of amylacetoacetatewere added and the mixture was heated at 80° C. for a further 2 hours. Abrown oil was obtained which, when taken up in 200 ml ofN-methylpyrrolidone, gave a weight of 276 g and was employed directlyfor the coupling reaction was obtained. A sample which was concentratedunder 0.5 mbar/100° C. gave the following mass spectrum:

MS, m/z (%) 376 (12) M⁺. !, 262 (8), 236 (11), 219 (18), 218 (21), 193(11), 192 (45), 151 (30), 55 (35), 43 (100)

The dyestuffs listed below, which likewise dyed polyester with goodfastness properties, were obtained by a coupling reaction analogously toExample 32.

                  TABLE 4                                                         ______________________________________                                         ##STR100##                                                                                                   Colour shade                                  Ex. No.                                                                             D               λ.sub.max (nm)                                                                   on polyester                                  ______________________________________                                        61                                                                                   ##STR101##     515 (CH.sub.3 CN)                                                                       Bluish-tinged red                             62                                                                                   ##STR102##     516 (CH.sub.3 CN)                                                                       Bluish-tinged red                             63                                                                                   ##STR103##     485 (CH.sub.3 CN)                                                                       Orange                                        64                                                                                   ##STR104##     483 (CH.sub.3 CN)                                                                       Orange                                        65                                                                                   ##STR105##     512 (CH.sub.3 CN)                                                                       Red                                           ______________________________________                                    

Example 66

Preparation of the coupler component of the formula ##STR106## wasprepared analougously to Ivanov J. C. et al., Liebigs Ann. Chem. 1983,753-60 and Mittelbach M. und Juneck H. Liebigs Ann. Chem. 1986, 533-544,by reaction of ethyl 3-amino-ethoxy-2-propenoate hydrochloride withamylcyanoacetate in chloroform in the presence of triethylamine. Furtherreaction with ethyl acetoacetate analogously to Example 33 gave thecoupler component of the above formula.

Example 67

Preparation of the dyestuff of the formula ##STR107##

The dyestuff of the above formula was obtained by diazotization of2-nitro-4-methoxyaniline in hydrochloric acid with 30% strength nitritesolution at 0° C. and subsequent coupling with the coupling componentaccording to Example 66. It dyed polyester in a brilliant red with goodfastness properties.

MS, m/z (%): 514 (28), M⁺ +H!, 513 (100) M⁺ ! 399 (12), 370 (26), 168(29), 43 (36)

λ_(max) : 515 nm (CH₃ CN)

Example 68

Preparation of the mixture of couplers of the formula ##STR108##

395 g of diamyl 3-amino-2-cyano-pentenedioate (78.7% according to GC)were heated together with 258 ml of ethyl acetoacetate and 154 ml ofdiazobicycloundecane at 80° C./60 mbar for 8 hours, readily volatilecomponents being destilled off. The excess acetoacetic ester wasdistilled off under 0.5 mbar/100° C. The brown oil (644 g) whichremained was employed directly for the coupling reaction.

MS, m/z (%): 376 (14), M⁺. !, 334 (5) M⁺. !, 307 (5), 262 (12), 219(23), 218 (22), 193 (15), 192 (67), 151 (48), 137 (20), 126 (27), 123(27), 98 (19), 96 (17), 71 (20), 55 (33), 43 (100)

The dyestuff of the formula ##STR109## listed on the following Table 5were obtained by coupling analogously to Example 32 with couplingcomponents which are accessible analogously to the Examples 33, 60, and68.

                                      TABLE 5                                     __________________________________________________________________________                                       Shade                                      Ex.                           λ.sub.max                                                                   on                                         No.                                                                              D          R.sup.1                                                                             R.sup.2                                                                             R.sup.3                                                                           (nm) polyester                                  __________________________________________________________________________    69                                                                                ##STR110##                                                                              C.sub.5 H.sub.11                                                                    C.sub.5 H.sub.11 80                                                                 CH.sub.3 20                                                                       515 (CH.sub.3 CN)                                                                  Bluish-tinged red                          70                                                                                ##STR111##                                                                              C.sub.5 H.sub.11                                                                    C.sub.5 H.sub.11 85                                                                 C.sub.2 H.sub.5 15                                                                515 (CH.sub.3 CN)                                                                  Bluish-tinged red                          71                                                                                ##STR112##                                                                              C.sub.5 H.sub.11                                                                    C.sub.5 H.sub.11 85                                                                 C.sub.2 H.sub.5 15                                                                516 (CH.sub.3 CN)                                                                  Bluish-tinged red                          72                                                                                ##STR113##                                                                              C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9 80                                                                  CH.sub.3 20                                                                       515 (CH.sub.3 CN)                                                                  Bluish-tinged red                          73                                                                                ##STR114##                                                                              C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9 80                                                                  CH.sub.3 29                                                                       516 (CH.sub.3 CN)                                                                  Bluish-tinged red                          74                                                                                ##STR115##                                                                              C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9 80                                                                  C.sub.2 H.sub.5 20                                                                515 (CH.sub.3 CN)                                                                  Bluish-tinged red                          75                                                                                ##STR116##                                                                              C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9 80                                                                  C.sub.2 H.sub.5 20                                                                516 (CH.sub.3 CN)                                                                  Bluish-tinged red                          76                                                                                ##STR117##                                                                              C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9 80                                                                  C.sub.2 H.sub.5 20                                                                     Rot                                        77                                                                                ##STR118##                                                                              C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9 80                                                                  C.sub.2 H.sub.5 20                                                                     Red                                        78                                                                                ##STR119##                                                                              C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9 80                                                                  C.sub.2 H.sub.5 20                                                                     Red                                        79                                                                                ##STR120##                                                                              C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9 80                                                                  C.sub.2 H.sub.5 20                                                                     Ruby                                       80                                                                                ##STR121##                                                                              C.sub.3 H.sub.7                                                                     C.sub.3 H.sub.7 80                                                                  C.sub.2 H.sub.5 20                                                                515 (CH.sub.3 CN)                                                                  Bluish-tinged red                          81                                                                                ##STR122##                                                                              C.sub.2 H.sub.5                                                                     C.sub.4 H.sub.9 80                                                                  C.sub.4 H.sub.9 20                                                                516 (CH.sub.3 CN)                                                                  Bluish-tinged red                          82                                                                                ##STR123##                                                                              CH.sub.3                                                                            C.sub.4 H.sub.9 80                                                                  C.sub.4 H.sub.9 20                                                                515 (CH.sub.3 CN)                                                                  Bluish-tinged red                          83                                                                                ##STR124##                                                                              C.sub.6 H.sub.13                                                                    C.sub.6 H.sub.13 80                                                                 C.sub.2 H.sub.5 20                                                                515 (CH.sub.3 CN)                                                                  Bluish-tinged red                          84                                                                                ##STR125##                                                                              C.sub.8 H.sub.17                                                                    C.sub.8 H.sub.17 85                                                                 C.sub.2 H.sub.5 15                                                                515 (CH.sub.3 CN)                                                                  Bluish-tinged red                          85                                                                                ##STR126##                                                                              C.sub.2 H.sub.4 OCH.sub.3                                                           C.sub.2 H.sub.4 OCH.sub.3 90                                                        CH.sub.3 10                                                                       515 (CH.sub.3 CN)                                                                  Bluish-tinged red                          86                                                                                ##STR127##                                                                              C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                    C.sub.2 H.sub.4 OC.sub.2 H.sub.5 90                                                 C.sub.2 H.sub.5 10                                                                515 (CH.sub.3 CN)                                                                  Bluish-tinged red                          __________________________________________________________________________

Example 87

Preparation of the dyestuffs of the formula ##STR128##

The coupling component was prepared by reaction ofdimethylacetonedicarboxylate with dimethyl 3-amino-2-cyano-pentenedioatein the presence of DBU at 100° C. analogously to Example 68. Couplingwith diazotized 2-nitro-4-ethoxyaniline gave the dyestuff of the aboveformula.

MS, m/z (%): 515 (100) M⁺. !, 516 (27), 457 (20), 456 (19), 425 (8), 424(36), 153 (12)

The dyestuff dyed polyester in a bluish-tinged red with good fastnessproperties.

Example 88

Preparation of the dyestuff of the formula ##STR129##

The coupling component was prepared analogously to Example 68 byreaction of ethyl benzoylacetate with diamyl3-amino-2-cyano-pentenedioate. Subsequent coupling with diazotized2-nitro-4-methoxyaniline in methanol gave the dyestuff of the aboveformula in crystalline form.

The dyestuff dyed polyester in a bluish-tinged red with good fastnessproperties.

MS, m/z (%): 514 (28) M⁺. +H!, 513 (100) M⁺. !, 471 (6), 443 (6), 399(12), 370 (26), 168 (29), 43 (36)

λ_(max) : 497 nm (CH₃ CN)

The following dyestuffs of the formula ##STR130## were obtainedanalogously to Example 88.

                  TABLE 6                                                         ______________________________________                                        Ex. No.                                                                             D                λ.sub.max                                                                       Shade on polyester                            ______________________________________                                        89                                                                                   ##STR131##      470 (CH.sub.3 CN)                                                                      Scarlet                                       90                                                                                   ##STR132##      493 (CH.sub.3 CN)                                                                      Red                                           91                                                                                   ##STR133##               Bluish-tinged red                             ______________________________________                                    

Example 92

Preparation of the coupler of the formula ##STR134##

49.5 g of 3-amino-2-methoxycarbonyl-2-pentenedinitrile (H. Junek et al.,Synthesis 1977, 560) were heated at the boiling point under reflux with47 g of ethyl acetoacetate and 30.6 g of piperidine in 300 ml of ethanolfor 13 hours. After cooling, the mixture was diluted to a volume of 1.8l with ice-water and brought to pH=2 with concentrated hydrochloricacid, and the product was filtered off with suction and washed withwater. Yield 59 g.

MS, m/z (%): 232 (5), 231 (24) M⁺. !, 187 (42), 172 (36), 160 (14), 144(21), 132 (13), 92 (26), 91 (29), 84 (23), 59 (100)

¹ H-NMR (d₆ -DMSO, 300 MHz, ppm): δ=2.15 (s, 3H, CH₃), 3.60 (s, 3H,OCH₃), 5.70 (s, 1H, 5-H), 8.25 (s, (br), 1H, N--H), 12.65 (s, 1H, O--H)

The following dyestuffs of the formula ##STR135## were preparedanalogously to Example 32 using coupling components of Example 92 orhomologous coupling components.

                  TABLE 7                                                         ______________________________________                                                                              Shade on                                Ex. No.                                                                             D               R       λ.sub.max                                                                      polyester                               ______________________________________                                        93                                                                                   ##STR136##     CH.sub.3                                                                              520 (CH.sub.3 CN)                                                                     Bluish- tinged red                      94                                                                                   ##STR137##     CH.sub.3        Ruby                                    95                                                                                   ##STR138##     C.sub.4 H.sub.9 Bluish- tinged red                      96                                                                                   ##STR139##     C.sub.5 H.sub.11                                                                              Bluish- tinged red                      97                                                                                   ##STR140##     CH.sub.3        Orange                                  98                                                                                   ##STR141##     CH.sub.3                                                                              443 (NMP)                                                                             Scarlet                                 99                                                                                   ##STR142##     CH.sub.3        Ruby                                    ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        Dyestuffs of the formula                                                       ##STR143##                                                                                                        Shade on                                 Ex. No.                                                                              D             R        λ.sub.max                                                                     polyester                                ______________________________________                                        100                                                                                   ##STR144##   C.sub.2 H.sub.5 Bluish- tinged red                       101                                                                                   ##STR145##   C.sub.2 H.sub.5                                                                        522 (NMP)                                                                            Red                                      102                                                                                   ##STR146##   C.sub.2 H.sub.5 Bluish- tinged red                       103                                                                                   ##STR147##   C.sub.2 H.sub.5 Reddish- tinged orange                   104                                                                                   ##STR148##   C.sub.2 H.sub.5                                                                        487 (CH.sub.3 CN)                                                                    Reddish- tinged orange                   105                                                                                   ##STR149##   C.sub.5 H.sub.11                                                                              Bluish- tinged red                       106                                                                                   ##STR150##   C.sub.6 H.sub.13                                                                              Bluish- tinged red                       ______________________________________                                    

Example 107

Preparation of the coupler of the formula ##STR151##

The preparation proceeded analogously to Example 66 by reaction of ethyl3-amino-4,4-dicyano-3-butenoate (Mittelbach M. and Junek H., LiebigsAnn. Chem. 1986, 533-544) with ethyl acetoacetate.

Example 108

Preparation of the mixture of the couplers of the formula ##STR152##

0.25 mol of diethyl 3-amino-2-cyano-pentenediaote ("dimeric ethylcyanoacetate"), 0.35 mol of methyl trifluoroacetoacetate and 0.25 mol ofdiazabicycloundecene were heated at 120° C. in 250 ml ofdimethylformamide for 12 hours. The solution was topped up to 400 mlwith dimethylformamide and employed directly for the coupling reaction.A concentrated sample gave the following mass spectrum.

MS, m/z (%): 346 (1) M⁺. X=CO₂ C₂ H₅ !, 301 (2), 275 (3), 274 (9), M⁺.X═H!, 255 (7), 246 (5), 203 (11), 202 (89), 184 (14), 173 (20), 152(44), 123 (27), 96 (27), 29 (100)

                  TABLE 9                                                         ______________________________________                                         ##STR153##                                                                                                            Shade                                Ex.                                 λ.sub.max                                                                   on poly-                             No.  D              X          R    (nm) ester                                ______________________________________                                        108                                                                                 ##STR154##    H (90) CO.sub.2 C.sub.2 H.sub.5 (10)                                                     C.sub.2 H.sub.5                                                                    511  Bluish- tinged red                   109                                                                                 ##STR155##    H (90) CO.sub.2 C.sub.2 H.sub.5 (10)                                                     C.sub.2 H.sub.5                                                                    512  Bluish- tinged red                   110                                                                                 ##STR156##    H (95) CO.sub.2 CH.sub.3 (5)                                                             CH.sub.3                                                                           486  Orange                               111                                                                                 ##STR157##    H (95) CO.sub.2 CH.sub.3 (5)                                                             CH.sub.3                                                                           474  Orange                               112                                                                                 ##STR158##    H (100)    CH.sub.3  Bluish- tinged red                   ______________________________________                                    

MS, m/z (%): 409 (24), 408 (100) M⁺. !, 275 (6), 135 (12), 120 (19), 108(27), 93 (17), 5 (11), 58 (17)

¹ H-NMR (d₆ -DMF, 300 MHz, ppm): δ=1.5 (t, 3H, OCH₂ --CH₃), 3.94 (s, 3H,--OCH₃), 4.3 (q, 2H, OCH₂ --CH₃), 7.04 (s, 1H, hetaromatic H), 7.18 (m,1H, aromatic H), 7.30 (m, 2H, aromatic H), 7.70 (d, 1H, aromatic H),11.95 (s/br), 1H, N--H), 14.75 (s, 1H, OH or NH).

Example 113

Preparation of the dyestuff of the formula ##STR159##

A solution of 18.6 g of ethyl (2'-nitro-4'-ethoxy)-2-phenylazo-formylacetate, 13.6 g of diethyl 3-amino-2-cyanopentenedioate and 9.1 g ofdiazabicycloundecene (DBU) in 60 ml of dimethylformamide was heated at80° C. for 30 minutes. It was diluted with 120 ml of ethanol, 7.3 g of30% strength hydrochloric acid and 18 ml of water. The precipitateformed was filtered off with suction and washed with ethanol. Thedyestuff dyes polyester in a bluish-tinged red with good fastnessproperties.

UV: 520 nm (CH₃ CN), 538 nm (DMF)

Example 114

Preparation of the coupler of the formula ##STR160##

A solution of 7.8 g of 2-amino-3-cyanoindene, 6.8 g of sodium ethylateand 7.8 g of ethyl acetoacetate in 100 ml of ethanol was heated at theboiling point under reflux for 7 hours. The mixture was filtered withsuction, the residue was dissolved in water, the solution was brought topH=1 with hydrochloric acid and the product was filtered off withsuction again.

MS, m/z (%): 222 (100) M⁺. !, 221 (5), 194 (6), 193 (10), 179 (7), 166(7), 140 (4), 139 (4), 84 (8), 67 (5), 38 (5)

                  TABLE 10                                                        ______________________________________                                        Dyestuffs of the formula                                                       ##STR161##                                                                                           λ.sub.max                                                                        Shade on                                    Ex. No.  D              (nm)      polyester                                   ______________________________________                                        115                                                                                     ##STR162##    469 (CH.sub.3 CN)                                                                       Red-brown                                   116                                                                                     ##STR163##              Claret                                      ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                        Dyestuffs of the formula                                                       ##STR164##                                                                                           λ.sub.max                                                                       Colour shade                                 Ex. No.  D              (nm)     on polyester                                 ______________________________________                                        117                                                                                     ##STR165##             Orange                                       118                                                                                     ##STR166##             Scarlet                                      119                                                                                     ##STR167##             Orange                                       ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                        Dyestuffs of the formula                                                       ##STR168##                                                                                           λ.sub.max                                                                       Colour shade                                 Ex. No.  D              (nm)     on polyester                                 ______________________________________                                        120                                                                                     ##STR169##    415 (CH.sub.3 CN)                                                                      Greenish-tinged yellow                       121                                                                                     ##STR170##    562 (DMF)                                                                              Claret                                       ______________________________________                                    

Example 122

Preparation of the coupler of the formula ##STR171##

4.3 g of 1-methyl-6-chloro-pyrid-2-one were added to a suspension of 1.8g of 80% strength sodium hydride in 30 ml of dimethylformamide, and 8.5g of butyl cyanoacetate were added dropwise in the course of 15 minutes.The temperature rose to 50° C. The mixture was stirred at 50° C. for afurther 7 hours, cooled to 20° C. and diluted slowly to a volume of 200ml with water. The mixture was brought to pH=7 with hydrochloric acidand extracted with methylene chloride. This extract was discarded. Theaqueous phase was brought to pH=4 and extracted again with methylenechloride. This extract was dried and concentrated.

Yield: 2.0 g of oil.

MS, m/z (%): 249 (8), 248 (43) M⁺. !, 151 (12), 148 (100), 147 (11), 121(16), 119 (22), 108 (20), 57 (74), 63 (41)

                  TABLE 13                                                        ______________________________________                                        Dyestuffs of the formula                                                       ##STR172##                                                                                           λ.sub.max                                                                        Colour shade                                Ex. No.  D              (nm)      on polyester                                ______________________________________                                        123                                                                                     ##STR173##              Scarlet                                     124                                                                                     ##STR174##    515 (CH.sub.3 CN)                                                                       Bluish-tinged red                           125                                                                                     ##STR175##              Orange                                      ______________________________________                                    

Example 126

Preparation of the coupler of the formula ##STR176##

21.8 g of 2-cyanomethyl-benzothiazole and 18 g of6-chloro-1-methyl-pyrid-2-one were added to a solution of 5 g of sodiumhydroxide powder in 125 ml of dimethylformamide and the mixture wasstirred at 40° C. for 6 hours. A further 1.8 g of6-chloro-1-methyl-pyrid-2-one were subsequently added and the mixturewas stirred at 40° C. for a further 8 hours. 300 ml of methylenechloride were added and the mixture was discharged onto 400 ml of water.5.5 g of a crystalline crude product were filtered off with suction, themethylene chloride phase was discarded and the aqueous phase was broughtto pH=5, after which a precipitate (B) again precipitated out, thisbeing filtered off with suction and washed with water: 7.8 g yield (B).

MS, m/z (%): 282 (27), 281 (100) M⁺. !, 241 (20), 148 (91), 108 (50), 39(51)

                  TABLE 14                                                        ______________________________________                                        Dyestuffs of the formula                                                       ##STR177##                                                                                           λ.sub.max                                                                       Colour shade                                 Ex. No.  D              (nm)     on polyester                                 ______________________________________                                        127                                                                                     ##STR178##             Claret                                       128                                                                                     ##STR179##             Claret                                       ______________________________________                                    

Example 129

Preparation of the coupler of the formula ##STR180##

A mixture of 37.4 g of 2,6-dichloropyridine and 47.5 ml of dimethylsulphate was stirred at 100° C. for 24 hours. After cooling, it wasdiluted with 75 ml of dimethylformamide, and a solution of 16.5 g ofmalononitrile in 25 ml of dimethylformamide and then 86.6 ml oftriethylamine were added dropwise, while cooling with ice. The mixturewas subsequently stirred for 20 hours and 14.7 g of a yellow product ofthe formula ##STR181## were then filtered off with suction. A further 4g were to be obtained by dilution of the filtrate with ice-water andacidification to pH=1.

MS (CI), m/z (%): 194 (35), 192 (100) M⁺. !, 158 (32)

76.6 g of 1-methyl-6-chloro-2(1)-pyridinylidene!malononitrile werestirred in 400 ml of water and 400 ml of N-methylpyrrolidone at 80° C.for 10 hours and at 90° C. for 5 hours, pH=10 being maintained bydropwise addition of 30% strength sodium hydroxide solution via atitrator. The mixture was topped up to a volume of 1200 ml with waterand brought to pH=1 with concentrated hydrochloric acid, and the productwas filtered off with suction and washed with water. Yield: 63.5 g.

MS, m/z (%): 173 (100) M⁺. !, 146 (25), 145 (37), 144 (37), 130 (14),119 (25), 118 (33), 108 (45), 39 (58).

¹ H-NMR (d₆ -DMSO, 300 MHz, ppm): δ=3.73 (s, 3H, N--CH₃), 6.15 (d, I=7.5Hz, 1H, 5-H), 6.53 (d, I=7.5 Hz, 1H, 3-H), 7.48 (dd, I=7.5 Hz, 1H, 4-H),11.80 (s(br), OH, H₂ O).

                  TABLE 15                                                        ______________________________________                                        Dyestuffs of the formula                                                       ##STR182##                                                                                            λ.sub.max                                                                       Colour shade                                Ex. No.                                                                             D                  (nm)     on polyester                                ______________________________________                                        130                                                                                  ##STR183##        516 (CH.sub.3 CN)                                                                      Bluish-tinged red                           131                                                                                  ##STR184##        517 (CH.sub.3 CN)                                                                      Bluish-tinged red                           132                                                                                  ##STR185##                 Orange                                      133                                                                                  ##STR186##        490 (CH.sub.3 CN)                                                                      Scarlet                                     134                                                                                  ##STR187##                 Orange                                      135                                                                                  ##STR188##        498 (CH.sub.3 CN)                                                                      Yellow-tinged red                           136                                                                                  ##STR189##        485 (CH.sub.3 CN)                                                                      Orange                                      137                                                                                  ##STR190##                 Orange                                      138                                                                                  ##STR191##        477 (CH.sub.3 CN)                                                                      Orange                                      139                                                                                  ##STR192##                 Scarlet                                     ______________________________________                                    

                  TABLE 16                                                        ______________________________________                                        Dyestuffs of the formula                                                       ##STR193##                                                                                                              Colour                                                                        shade                              Ex.                                 λ.sub.max                                                                     on poly-                           No.  D              A.sup.1                                                                              A.sup.2                                                                           A.sup.5                                                                            (nm)   ester                              ______________________________________                                        140                                                                                 ##STR194##    H      H   C.sub.2 H.sub.5                                                                    516 (CH.sub.3 CN)                                                                    Bluish- tinged red                 141                                                                                 ##STR195##    CH.sub.3                                                                             H   CH.sub.3                                                                           508    Yellow- ish tinged red             142                                                                                 ##STR196##    CH.sub.3                                                                             CN  CH.sub.3    Bluish- tinged red                 143                                                                                 ##STR197##    H      H   C.sub.3 H.sub.7                                                                    516    Bluish- tinged red                 144                                                                                 ##STR198##    H      H   C.sub.4 H.sub.9                                                                    516    Bluish- tinged red                 ______________________________________                                    

                  TABLE 17                                                        ______________________________________                                        Dyestuffs of the formula                                                       ##STR199##                                                                                            λ.sub.max                                                                       Colour shade                                Ex. No.   D              (nm)     on polyester                                ______________________________________                                        145                                                                                      ##STR200##             Red                                         146                                                                                      ##STR201##             Red                                         147                                                                                      ##STR202##             Red                                         148                                                                                      ##STR203##             Red                                         ______________________________________                                    

Example 149

Preparation of a coupler ##STR204##

15.7 g of benzenesulphonamide were added to a solution of 5.4 g ofsodium methylate in 120 ml of methanol and the mixture was boiled underreflux for 2 hours, the benzenesulphonamide dissolving. The solution wasconcentrated to dryness, the residue was dissolved in 75 ml ofN-methylpyrrolidone and a solution of 19.2 g of1-methyl-6-chloro-2(1H)-pyridinylidene!malononitrile (see Example 129)in 75 ml of N-methylpyrrolidone was allowed to run in. After 20 hours atroom temperature, a further 2.7 g of sodium methylate and 3.9 g ofbenzenesulphonamide were added and the mixture was heated at 50° C. for5 hours and stirred at room temperature for 60 hours. It was dilutedwith 600 ml of ice-water and brought to pH=1 with hydrochloric acid, andthe product was filtered with suction and washed with water. Yield 15 g.

¹ H-NMR (d₆ -DMSO, 300 MHz, ppm): δ=3.75 (s, 3H, N--CH₃), 6.38 (d, I=7.5Hz, 1H, heterocyclic H), 6.45 (d, I=7.5 Hz, 1H, heterocyclic H), 7.30(dd, I=7.5 Hz, 1H, heterocyclic H), 7.53 (m, 3H, aromatic H), 7.78 (m,2H, aromatic H), 9.48 (s(br), 1H, N--H).

                  TABLE 18                                                        ______________________________________                                        Dyestuffs of the formula                                                       ##STR205##                                                                                            λ.sub.max                                                                      Colour shade                                 Ex. No.  D               (nm)    on polyester                                 ______________________________________                                        150                                                                                     ##STR206##             Bluish-tinged red                            151                                                                                     ##STR207##             Yellowish- tinged red                        ______________________________________                                    

Example 152

10 g of polyester fabric are introduced at a temperature of 60° C. into200 ml of a dye liquor which comprises 0.3% of the finely disperseddyestuff of Example No. 134, based on the polyester fabric, and in whichthe pH is adjusted to 4.5 by means of acetic acid. The fabric is treatedat 60° C. for 5 minutes, the temperature of the liquor is then increasedto 135° C. in the course of 30 minutes and kept at this temperature for60 minutes, and the liquor is then allowed to cool to 60° C. in thecourse of 20 minutes.

Thereafter, the dyed polyester fabric is purified reductively by beingtreated at 10 65° C. for 15 minutes in 200 ml of a liquor whichcomprises 5 ml/l of 32% strength by weight sodium hydroxide solution, 3g/l of sodium dithionite and 1 g/l of an addition product of 48 ml ofethylene oxide on 1 mol of castor oil. Finally, the fabric is rinsed,neutralized with dilute acetic acid, rinsed again and dried. A brilliantorange dyeing with good fastness properties is obtained.

What is claimed is:
 1. A dyestuff of the formula ##STR208## or itstautomeric form wherein D is a radical selected from the groupconsisting of: ##STR209## wherein R¹, R², R³, R⁴, R⁵ and R⁶independently of one another represent H, T, F, Cl, Br, I, --CN, --NO₂,--CH═O, --COT, --CO₂ T¹, --CONH₂, --CONHT, CONT₂, --CF₃, --SO₂ NH₂,--SO₂ NHT, --SO₂ NT₂, --SOT, --SO₂ T, --SO₃ T, --OT, --OH, --OCOT,--OCO₂ T, --OSO₂ T, --NH₂, --NHT, --NT₂, ##STR210## --NHCOH --NHCOT,--NHSO₂ T and --COCO₂ T, wherein R³ also represents --N═N--T⁴ or N═N--T⁵andR⁶ also represents ST, A¹ and A² independently of one another denoteH or a radical selected from the group consisting of T, --COH, --CO--T,--CO₂ T, --CN, --CONH₂, --CONHT, --CONT₂, CF₃,--NH₂, --NHT, --NT₂,--NH--COT, --NT--COT, --NHSO₂ T, --NTSO₂ T, --NO₂, --NO, --SOT, --OH,--OT, --OCOT, --OCO₂ T, --OSO₂ T, Cl, Br and I A³ and A⁴ independentlyof one another represent --CN, --CO₂ T, --CONH₂, --CONHT, --CONT₂, CF₃,--CHO, --COT, --SO₂ T, --SO₃ T⁴, --SO₃ T⁵, SO₂ NH₂, SO₂ NHT, SO₂ NT₂,--SOT, --CH═NH, --CH═NT, --CT═NH, --CT═NT, ##STR211## --CO--CO₂ T,--NO₂, --NO, T⁴ or T⁵, or A³ and A⁴, together with the C atom to whichthey are bonded, represent a cyclic methylene-active compound of theformula (IIa) to (IIv), wherein the radicals are represented by##STR212## and wherein the compound of the formula (IIa) to (IIv) isselected from the group consisting of ##STR213## wherein V¹ representsH, Cl, Br, CH₃, --CO₂ T¹, --CN, --NO₂, --CF₃ or --SO₂ T¹, A⁵ representsH or a radical of the formula T, --OT¹, --NH₂, --NHT, --NT₂, --NHCOH,--NHCOT, --N═CH--T, --N═CT₂ or NHSO₂ T, wherein T represents T¹ to T⁵ T¹represents C₁ -C₂₀ -alkyl, C₄ -C₈ cycloalkyl or C₆ -C₁₀ -aryl-C₁ -C₈-alkyl, each of which is unsubstituted or substituted by one or moresubstituents selected from the group consisting of ##STR214## --OCOH,COH, --OCOT, --OSO₂ T, --O(CH₂ C ₂ O)₁₋₆ COT, --OCO₂ T, COT, --SO₂ T,--CO₂ T, --CN, --CONH₂, --CONHT, --CONT₂, --CO₂ H, --SO₂ NH₂, --SO₂ NHT,--SO₂ NT₂, --CF₃, --NO₂ and halogen, T² and T³ represents C₂ -C₂₀-alkenyl or C₂ -C₂₀ -alkinyl, each of which is unsubstituted orsubstituted by one or more substituents selected from the group ofsubstituents as in T¹ T⁴ represents C₆ -C₁₆ -aryl which is unsubstitutedor substituted by one or more substituents selected from the groupconsisting of ##STR215## --OCOH, COH, --OCOT, --OSO₂ T, --O(CH₂ CH₂O)₁₋₆ COT, --OCO₂ T, COT, --SO₂ T, --CO₂ T, --CN, --CONH₂, --CONHT,--CONT₂, --CO₂ H, --SO₂ NH₂, --SO₂ NHT, --SO₂ NT₂, --CF₃, --NO₂ andhalogen, --NH₂, --NHT, --NT₂, --NHCOH, --NHCOT, NHSO₂ T, C₂ -C₁₀-alkenyl, C₂ -C₁₀ -alkinyl, C₁ -C₁₀ -alkyl, C₄ -C₈ -cycloalkyl and C₆-C₁₀ -aryl-C₁ -C₆ -alkyl; T⁵ represents thiophene, furan, pyrrole,1,2-isothiazole, 1,3-thiazole, pyrrazole, oxazole, isooxazole,imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine,triazine, oxazine, benzothiazole, benzimidazole, benzoxazole, quinoline,isoquinoline, indole, coumarone, thionaphthene or tetrazole, each ofwhich are unsubstituted or substituted one or more times by substituentsselected from the group consisting of ##STR216## --OCOH, COH, --OCOT,--OSO₂ T, --O(CH₂ CH₂ O)₁₋₆ COT, --OCO₂ T, COT, --SO₂ T, --CO₂ T, --CN,--CONH₂, --CONHT, --CONT₂, --CO₂ H, --SO₂ NH₂, --SO₂ NHT, --SO₂ NT₂,--CF₃, --NO₂ and halogen, --NH₂, --NHT, --NT₂, --NHCOH, --NHCOT, NHSO₂T, C₂ -C₁₀ -alkenyl, C₂ -C₁₀ -alkinyl, C₁ -C₁₀ -alkyl, C₄ -C₈-cycloalkyl and C₆ -C₁₀ -aryl-C₁ -C₆ -alkyl, or A¹ and A² together withthe particular atoms in between, form an unsaturated unsubstituted orsubstituted 6-membered carbocylic radical, A² and A³ independently ofone another represent --CN, --CO₂ T, --CONH₂, --CONHT, --CONT₂, CF₃,--CHO, COT, --SO₂ T, --SO₃ T⁴, --SO₃ T⁵, SO₂ NH₂, SO₂ NHT, SO₂ NT₂,--SOT, --CH═NH, --CH═NT, --CT═NH, --CT═NT, --CO--COT, --NO₂, --NO, T⁴ orT⁵⁻ or A⁴ and A⁵ together with the atoms of the pyridone ring inbetween, form a fused ring of the formula ##STR217## wherein the N atomlabelled with * corresponding to the pyridone nitrogen, X represents O,NH, NT, NCOT, NCO₂ T or NSO₂ T, K⁺ is --NH₃ ⁺, --NHT₂ ⁺, --NH₂ T⁺, --NT₃⁺ or a cycloimmonium ion, B⁻ represent an organic or inorganic anion, Zrepresents --CH═CH₂ or --CH₂ CH₂ --V wherein, V represents OH, OSO₃ H,SSO₃ H, OCOCH₃, OPO₃ H₂, SCN, NHSO₂ CH₃, Cl, Br, F, OCOC₆ H₅, OSO₂ --C₆H₄, N(CH₃)₃ !⁺ anion⁻ or an unsubstituted or substituted pyridiniumradical wherein the substituents are selected from the group consistingof C₁ -C₄ -alkyl, COOH, SO₃ H, CN and carboxamide or a heterocyclicfiber-reactive radical wherein said radical is 2,4-difluorotriazin-6-yl,2,4-dichlorotriazin-6-yl and monohalogeno-sym-triazinyl radicals whichare substituted by alkyl, aryl, amino, monoalkylamino, dialkylamino,aralkylamino, arylamino, morpholino, piperidino, pyrrolidino,piperazino, alkoxy, aryloxy, alkylthio or arylthio, where alkyl denotesoptionally substituted C₁ -C₄ -alkyl, aralkyl denotes unsubstituted orsubstituted phenyl-C₁ -C₄ -alkyl and aryl denotes unsubstituted orsubstituted phenyl or naphthyl, and the substituents for alkyl areselected from the group consisting of halogen, hydroxyl, cyano,dialkylamino, morpholino, C₁ -C₄ -alkoxy, carboxyl, sulpho and sulphato;the substituents for phenyl and naphthyl are selected from the groupconsisting of sulpho, C₁ -C₄ - alkyl, C₁ -C₄ -alkoxy, carboxyl, halogen,acylamino, hydroxyl and amino or said heterocyclic fiber-reactiveradicals are selected from the group consisting of2-amino-4-fluorotriazin-6-yl, 2-methylamino-4-fluorotriazin-6-yl,2-ethylamino-4-fluorotriazin-6-yl,2-isopropylamino-4-fluoro-triazin-6-yl,2-dimethylamino-4-fluorotriazin-6-yl,2-diethylamino-4-fluorotriazin-6-yl,2-β-methoxy-ethylamino-4-fluoro-triazin-6-yl,2-β-hydroxyethylamino-4-fluoro-triazin-6-yl,2-di-(β-hydroxyethylamino)-4-fluoro-triazin-6-yl,2-carboxymethylamino-4-fluoro-triazin-6-yl,2-di-(carboxymethylamino)-4-fluoro-triazin-6-yl,2-sulphomethyl-methylamino-4-fluoro-triazin-6-yl,2-β-cyanoethylamino-4-fluoro-triazin-6-yl,2-benzylamino-4-fluoro-triazin-6yl,2-β-phenylethylamino-4-fluoro-triazin-6-yl, 2-benzyl-methylamino-4-fluoro-triazin-6-yl,2-(4'-sulphobenzyl)-amino-4-fluoro-triazin-6-yl,2-cyclohexylamino-4-fluoro-triazin-6-yl, 2-(o-, m- orp-methylphenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- orp-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2,5'-disulphophenyl)-amino-4-fluoro triazin-6-yl, 2-o-, m- orp-chlorophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- orp-methoxyphenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-methyl-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-methyl-5'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-chloro-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-chloro-5'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-methoxy-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- orp-carboxyphenyl)-amino-4-fluoro-triazin-6-yl,2-(2',4'-disulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(3',5'-disulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-carboxy4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(2'-carboxy-5'-sulphophenyl)-amino-4-fluoro-triazin-6-yl,2-(6-sulpho-naphth-2'-yl)-amino-4-fluoro-triazin-6-yl,2-(4',8'-disulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl,2-(6',8'-disulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl,2-(N-methyl-N-phenyl)-amino-4-fluoro-triazin-6-yl,2-(N-ethyl-N-phenyl)-amino4-fluoro-triazin-6-yl,2-(N-β-hydroxyethyl-N-phenyl)-amino-4-fluoro-triazin-6-yl,2-(N-isopropyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-morpho-lino-4-fluoro-triazin-6-yl, 2-piperidino-4-fluoro-triazin-6-yl,2-(4',6',8'-trisulphonaphth-2'-yl)-amino-4-fluorotriazin-6-yl,2-(3',6',8'-trisulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl,2-(3',6'-disulphonaphth-1'-yl)-amino-4-fluoro-triazin-6-yl,N-methyl-N-(2,4-dichlorotriazin-6-yl)-carbamyl,N-methyl-N-(2-methylamino-4-chlorotriazin-6-yl)-carbamyl,N-methyl-N-(2-dimethylamino-4-chlorotriazin-6-yl) carbamyl, N-methyl- orN-ethyl-N-(2,4-dichlorotriazin-6-yl)-aminoacetyl,2-methoxy4-fluoro-triazin-6-yl, 2-ethoxy-4-fluoro-triazin-6-yl,2-phenoxy-4-fluoro-triazin-6-yl, 2-(o-, m- orp-sulphophenoxy)-4-fluoro-triazin-6-yl, 2-(o-, m- or p-methyl- or-methoxy-phenoxy)-4-fluoro-triazin-6-yl,2-β-hydroxyethylmercapto-4-fluoro-triazin-6-yl,2-phenylmercapto-4-fluoro-triazin-6-yl,2-(4'-methylphenyl)-mercapto-4-fluorotriazin-6-yl,2-(2',4'-dinitrophenyl)-mercapto-4-fluoro-triazin-6-yl,2-methyl-4-fluoro-triazin-6-yl, 2-phenyl-4-fluoro-triazin-6-yl and thecorresponding 4-chloro- and 4-bromotriazinyl radicals and thecorresponding radicals obtainable by exchange of halogen with a tertiarybase, selected from the group consisting of trimethylamine,triethylamine, dimethyl-β-hydroxyethylamine, triethanolamine,N,N-dimethylhydrazine, pyridine, α, β- or γ-picoline, nicotinic acid orisonicotinic acid, sulphinates, and di- or trihalogenopyrimidinylradicals l represents 0 to 2, m represents 0 to 8 and n represents 0 to6.
 2. The compound according to claim 1, wherein l is 1 or 2, n is 0 andm is 0 or
 1. 3. The compound according to claim 1, wherein l, m, and nare
 0. 4. The compound according to claim 1, wherein l is 0 and m and nare not
 0. 5. The compound according to claim 1, whereinl=m=n=0, A¹represents H, T, --COH, --COT, --CO₂ T, --CN, --CONH₂, --CONHT, --CONT₂,CF₃, OH or halogen, A² represents H, T, --COH, --COT, --CN, --CO₂ T,--CONH₂, --CONHT --CONT₂, --CF₃, --NO₂, --NO, Cl, Br or I, A³ and A⁴independently of one another represent --CN, --CO₂ T, --CONH₂, --CONHT,--CONT₂, CF₃, --CHO, --COT, --SO₂ T, --SO₃ T⁴, --SO₃ T⁵, SO₂ NH₂, SO₂NHT, SO₂ NT₂, --SOT, --CH═NH, --CH═NT, --CT═NH, --CT═NT, --CO--CO₂ T,--NO₂, --NO, T⁴ or T⁵, or A² and A³, together with the C atoms inbetween them, form the radical of a fused indene ring which isunsubstituted or substituted by R¹, or A⁵ denotes H, T¹, T², T³, T⁴,--NH₂, --NHT, NT₂, --NHCOT, --NHCOH, --NHSO₂ T or --N═CT₂ or X denotesO, --NCOT, --NCO₂ T or --NSO₂ T.
 6. The compound according to claim 1,whereinl=m=n=0 and A¹ represents H, T, --COH, --COT, --CO₂ T, --CN,--CONH₂, --CONHT, --CONT₂, --CF₃, OH, Cl, Br or I.
 7. The compoundaccording to claim 1, whereinl=m=n=0 and A³ and A⁴ independently of oneanother represent --CN, --CO₂ T, --CONH₂, --CONHT, --CONT₂, CF₃, --CHO,--COT, --SO₂ T, --SO₃ T⁴, --SO₃ T⁵, SO₂ NH₂, SO₂ NHT, SO₂ NT₂, --SOT,--CH═NH, --CH═NT, --CT═NH, --CT═NT, --CO--CO₂ T, --NO₂, --NO, T⁴ or T⁵,wherein A³ and A⁴ do not simultaneously represent T⁴ and/or T⁵.
 8. Thecompound according to claim 1, whereinl=m=n=0 and T⁴ denotes phenyl,which is unsubstituted or substituted by one or more substituents of thegroup consisting of --C₁ -C₁₀ -alkoxy-, ---(O-C₂ -C₁₀ -alkylene)₀₋₁--O--(C₂ -C₅ -alkylene)₁₋₆ -O-(C₂ -C₅ -alkyl); --OCOH; --OCOT; --OSO₂ T;--COH; --COT; --SO₂ T; --CO₂ T; --CN; --CF₃ ; --CCl₃ ; --NO₂ ; --NO;--CO₂ H; --CONH₂ ; --CONHT; --CONT₂ ; --SO₂ NT² ; --C₁ -C₁₀ -alkyl,unsubstituted or substituted by --OH, --CN, --CO₂ --C₁ -C₆ -alkyl, Cl,Br or I; --C₂ -C₁₀ -alkenyl, unsubstituted or substituted by --OH, --CN,--CO₂ --C₁ -C₆ -alkyl, Cl, Br or I; and --C₂ -C₁₀ -alkinyl,unsubstituted or substituted by C₁ -C₁₀ -alkoxy, --OH, --OCOH, --OCOT,Cl, Br or I.
 9. The compound according to claim 1, whereinl=m=n=0, A¹represents H, T¹ or --CF₃, A² denotes H, --CN or --CO₂ T¹, A³ represents--CN or --CO₂ T¹, A⁴ denotes A³, or A³ and A⁴, together with the C atomto which they are bonded, form a cyclic methylene-active compound of theformula (IIa) or (IId), where the radicals of the cyclicmethylene-active compound are shown in the form of ##STR218## A⁵represents H, T¹ or T², D represents a radical of the formula ##STR219##wherein R¹ and R⁵ independently of one another denote H, Cl, Br, --CN,--NO₂, --CO₂ T¹, T¹, --OT¹ or --OT⁴, R² and R⁴ independently of oneanother denote H, Cl, Br, --NO₂, T¹ or --OT¹, R³ represents H, Cl, Br,--CN, --NO₂, T¹, --CO₂ T¹ or --OT¹, T¹ represents C₁ -C₆ -alkyl or C₁-C₄ -T⁴, unsubstituted or substituted by C₁ -C₆ -alkoxy, --C₁ -C₄-alkoxy-C₂ -C₅ -alkoxy or --CO₂ T¹, T² denotes C₂ -C₆ -alkenyl which isunsubstituted or substituted by Cl or Br, T⁴ represents phenyl, which isunsubstituted or substituted by Cl, Br, --NO₂ and/or --CO₂ T¹ and Xdenotes
 0. 10. A process for the preparation of a compound according toclaim 1, wherein an amine of the formula

    D--NH.sub.2                                                (IV)

is diazotized and the diazotization products formed are coupled tocoupling components of the formula ##STR220## wherein A¹ and A⁵, D and Xhave the meaning given in claim 1 and E represents a substituent whichcan be replaced by H, --CO₂ H, --CH₂ OH, --SO₃ H, --CH═O, --COT,##STR221## --CONH₂ or --CONHT.
 11. A process for dyeing and printingnaturally occurring synthetic materials, wherein the dyestuff accordingto claim 1 is applied.
 12. The process according to claim 11 for dyeingand printing cellulose fibres, cotton, wool, silk, polyamide,polyacrylonitrile, polyester or polyolefins.
 13. A process for dyeingand printing hydrophobic synthetic fibre materials or mixtures thereofwith naturally occurring fibre materials wherein a dyestuff according toclaim 1 in which l=m=n=0 is applied.